CN102199433A - Coal carbonization technology with treating CO2 as temperature control component in combustion process - Google Patents
Coal carbonization technology with treating CO2 as temperature control component in combustion process Download PDFInfo
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- CN102199433A CN102199433A CN2011100583459A CN201110058345A CN102199433A CN 102199433 A CN102199433 A CN 102199433A CN 2011100583459 A CN2011100583459 A CN 2011100583459A CN 201110058345 A CN201110058345 A CN 201110058345A CN 102199433 A CN102199433 A CN 102199433A
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Abstract
The invention relates to a coal carbonization technology with treating CO2 as a temperature control component in a combustion process. A purpose of changing a raw coke oven gas component system into a poor nitrogen system can be achieved through replacing partial/all nitrogen as the temperature control component in routine coal carbonization technologies with CO2. The technology is particularly suitable for semicoke preparation, and semicoke, tar, hydrogen, natural gas, CO2, sulfur and a feed gas for methanol preparation can be produced by treating coal, water and oxygen as raw materials under a condition of basically not changing existing structures of carbonization equipment and operation conditions. The resource recovery rate, the purity, the flexibility of product quality adjustment and the stability of product quality control can be substantially improved, and energy consumption can be substantially reduced. The technology in the invention, which allows routine coal carbonization technologies for crude product preparation to be changed into chemical technologies for fine product prepareation, is a technical route of the coal chemical industry, can be used in new projects, and also can be used to modify previous projects.
Description
Technical field
The present invention relates to a kind of with CO
2Coal carbonization technology for combustion processes temperature control component; Say especially the present invention relates to a kind of with CO
2Circulation gas is the oxygen enrichment coal carbonization technology of combustion processes temperature control component; More particularly the present invention relates to a kind of with CO
2Oxygen enrichment coal system semicoke (blue charcoal) technology for combustion processes temperature control component, the combustion chamber temperature control component nitrogen that partly or entirely replaces conventional coal carbonization technology, under the prerequisite that does not change existing charing device structure and operational condition substantially, form the chemical industry type technology of production fine product, with coal, water, air is raw material, produces blue charcoal, tar, hydrogen, Sweet natural gas, CO
2Gas, sulphur can increase substantially resource value, increase substantially the handiness of regulating quality product, the remarkable stability that strengthens the control quality product simultaneously, reduce the process energy consumption, reduce plant investment, significantly increase economic benefit.
Background technology
As everyone knows, Anshan Thermal Energy Inst. of China Steel Group begins " is that raw material is at the special-purpose blue charcoal of vertical retort refining iron alloy with non-caking coal or weakly caking coal lump coal " technology (hereinafter to be referred as middle steel gas making technology BT) of constantly research and development the early 1980s, adopt and be fit to the coal source (such as Chinese Datong District, the geographic coal in refreshing mansion), the blue charcoal of refining and by-product raw gas and middle coalite tar in vertical retort, it is a kind of blue charcoal good quality of product, coal tar productive rate height, construction costs is lower, the mature industry technology that supporting green technology is perfect had obtained widely applying already.This technology has the general feature of similar blue charcoal technology: be oxygen donator with the air, the main body of combustion chamber temperature control component (non-flammable, non-oxidiser component that combustion processes exists) is a nitrogen, and the raw gas of generation is with CO
2-CH
4-CO-N
2(being generally the main body component)-H
2For representing the system of component, the raw gas component is separated when adopting the PSA industrial technology usually, and in the common process, the separation of raw gas system and utilization have following shortcoming:
1. a large amount of raw gas cause a large amount of hydrogen as fuel consumption, serious waste of resources as charring furnace fuel; When needs prepare hydrogen to greatest extent, there is the situation of making fuel with hydrogen and carbon monoxide in the time of with the hydrogen manufacturing of raw gas carbon monoxide, the utilization of resources is extremely unreasonable, causes increasing facility investment simultaneously, increases plant energy consumption;
2. because N
2A large amount of existence of component, there are a large amount of N in follow-up transformation adsorption separation process (as the hydrogen purification process) material of raw gas or raw gas CO conversion gas
2Component, and N
2Component and H
2It is right that component belongs to the last step separated portion, increased the volume of material scale of whole device, causes the increase of construction investment;
3. because N
2A large amount of existence of component, transformation adsorption separation process (as the hydrogen purification process) H of raw gas or CO conversion gas
2/ N
2, N
2/ CO, N
2/ CH
4Component between separation factor less, in order to guarantee hydrogen yield, need to improve working pressure, cause process compression work consume significant;
4. because N
2A large amount of existence of component, and with respect to other non-hydrogen component, N
2The adsorptive capacity of component on sorbent material is very little, and referring to table 1 column data, at the transformation adsorption separation process (as the hydrogen purification process) of raw gas or raw gas CO conversion gas, the sorbent quantity that needs is big, causes that equipment size is big, construction investment quantity is big;
5. because N
2A large amount of existence of component, transformation adsorption separation process (as the hydrogen purification process) H of raw gas or CO conversion gas
2/ N
2, N
2/ CO, N
2/ CH
4The component system separation factor is less, N
2The process that effluxes of component detachment system causes H inevitably
2With combustibleconstituents CH
4Deng emission loss;
6. because N
2A large amount of existence of component have produced or have increased charring furnace HCN product output, have increased the process of wet desulphurization load, cause the increase of solvent-oil ratio;
7. do not consider that raw gas transformation absorption puies forward the air-breathing depriving hydrogen sulphide problem of hydrogenolysis, cause hydrogen sulfide to discharge in a large number;
8. existing technology coking chamber charing section temperature is restricted (700～850 ℃), and must guarantee that the raw gas calorific value can not be lower than the Schwellenwert of regulation (such as 1600～1800kcal/Nm
3), but, because the character of different coals (such as volatile content, reactive height) difference, the variation of operation index is unavoidable, raw gas combustibleconstituents content is that calorific value fluctuates within the specific limits, when having to regulate its calorific value when raw gas calorific value improper (especially too low), because existing technology lacks raw gas calorific value regulating measure, blue carbonaceous amount often is affected.That is to say and use the conventional blue charcoal technology of nitrogen as combustion processes main body heat-carrying component, has " property the taken into account adjusting handiness of blue carbonaceous amount and caloric power of gas " relatively poor shortcoming, the popularization that this has limited blue charcoal technology to a certain extent that is to say the coal carbonization technology that needs exploitation a kind of " guaranteeing to possess flexible raw gas calorific value function under the blue carbonaceous amount prerequisite ";
When 9. the raw gas calorific value is low, raw gas transformation adsorption-desorption gas calorific value is lower, the not convenient time spent, the occasion that particularly blue charcoal unit scale hour, transformation absorption tail gas quantity is little, exist transformation adsorption-desorption gas to diffuse emptying, form energy dissipation, if that build means recovery such as power generation assembly then less economical; Power generation assembly needs the certain economic scale, is suitable for the big occasion of transformation absorption tail gas quantity.When the raw gas calorific value is too low, if for preparation high performance fuel gas be CO from the system component
2-CH
4-N
2-H
2Raw gas in separate N
2, because H
2/ N
2System separates needs higher pressure and more sorbent material, then " non-flammable heat-carrying component N
2Sepn process " need to consume a large amount of compression works, extensive pressure-swing absorption apparatus is set, investment and energy consumption are huge.At above-mentioned shortcoming, the improvement Journal of Sex Research of the Technology in (about 20 years) this coal carbonization field and test for many years concentrates on the poor nitrogenize aspect of combustion processes oxygenant mostly, almost all adopt oxygen enrichment or pure oxygen means, because oxygen enrichment or pure oxygen burning cause raw gas to become CO
2-CH
4The poor N of-CO-
2-H
2System, the combustion processes of the poor nitrogen raw gas of high heating value " the poor nitrogen oxygenant (oxygen enrichment or pure oxygen) with " causes temperature of combustion, combustionvelocity and conventional charring process " air and than the combustion processes of low heat value raw gas " difference too big, do not changing significantly under the prerequisite of existing charring furnace structure, be difficult to reach the stable conditions suitable (as 700～850 ℃ of the temperature of appropriateness, a large amount of gas thermophores) of the blue charcoal of production of conventional charring process, fail industrial applications always.With the middle steel gas making technology BT internal heat type coal carbonization that is representative produce semicoke (blue charcoal) technology be a kind of be charcoal processing, produce oil, the gas making combination producing technology of raw material with the coal, have following characteristics: charring furnace comprises fuel gas combustion chamber and coal carbonization chamber; Indoor in coal carbonization, according to the advance route of coal charge, being divided into first section is that coal preheating section (or claim gas cooling section), second section are that coal carbonization section (or claim combustion product gases and preheating after first via gas mixing section) and the 3rd section are charcoal cooling section (or title gas preheating section); In the 3rd section zone, the first via gas (normal temperature coal gas or coal gas and air Mixture) that comprises coking chamber heat-carrying component and two sections process material contact heat-exchangings reclaim to heat up behind its heat becomes three sections process gas, and three sections process material leave three sections zones; In second section zone, gas fume of combustion chamber, three sections process gas, with one section process material carry out gas-solid directly contact take place that charing does should (heating, evaporation, water-gas transform, the reactions such as steam reforming of charcoal), two sections process material leave second section zone and enter the 3rd section zone, and two sections process gas leave second section zone and enter first section zone; In first section zone, two sections process gas and coal charge Contact Heating coal charge transmit the heat postcooling and sneak into one section that to produce pneumatolytic be one section product gas (raw gas), become one section process material after coal charge heats up and enter second section zone.It is characterized in that: the combustion chamber oxygen donator is an air, with N
2Be the main temperature control component of combustion processes.
Above-mentioned charring furnace ST is a core research object of the present invention, charring furnace ST comprises combustion chamber and coking chamber, (or the part subsequent combustion of half flue gas, half flue gas is finished in the coking chamber space so that high-temperature flue gas to be provided to coking chamber in the combustion chamber, high-temperature flue gas of the present invention comprises half flue gas) mode heat energy is provided, coking chamber comprises blends preheating, coal carbonization, three processes of charcoal cooling, brings into play following effect when the circulation raw gas is as coking chamber heat-carrying component in the conventional charring process:
1. at the charcoal cooling section, contact hot charcoal and reclaim its heat energy;
2. in dry distillation of coal section, mix, participate in dry distillation of coal process with gas fume of combustion chamber;
3. at the coal preheating section, preheating coal charge (producing coal dewatering, degasifying effect)
4. at each section, carry vaporize water, tar steam, reaction generation gas etc.
By above analysis as can be known, as coking chamber gas heat-carrying component, guaranteeing that component has no adverse effects to technological process, and under the stable prerequisite of chemical property, its key property is thermal conduction study functional property such as thermal conductivity, unit volume specific heat etc., whether combustibleconstituents (it forms whether be equal to coal gas in other words) is unimportant, that is to say: at the thermal conduction study functional property such as the thermal conductivity that guarantee coking chamber gas heat-carrying component, under the prerequisite that unit volume specific heat etc. change within the specific limits, any technology that change is formed from ring coal gas substantially can not influence the reliability of coking chamber gas heat-carrying function, promptly can adapt to it by regulating coking chamber gas heat-carrying logistics quantity.In other words, by regulating the quantity and the composition of the logistics of coking chamber gas heat-carrying, can change (or allowing to change) coking chamber gas heat-carrying logistics composition just changes from ring coal gas composition, that is to say in order to change (improvement) and form, must change coking chamber gas heat-carrying logistics composition and quantity from ring coal gas.Core concept of the present invention is: do not change the combustion chambers burn characteristic substantially,, realize changing (improvements) purpose from ring coal gas composition by changing the logistics composition and the quantity of combustion chamber and coking chamber, and make it to possess economy, practicality.
The present invention uses following conceptual description coal carbonization device technique process:
1. gas making part: with coal, water, oxygen donator, fuel body is raw material, obtains charcoal, tar, from ring coal gas craft process, comprises that charring furnace ST and coal gas return stove part technological process;
2. gas making part internal recycle logistics: the recycle stream of gas making partial interior;
3. from ring coal gas processing part: the machining process that leaves the coal gas in coal gas internal recycle loop (promptly discharging the gas making part);
4. gas making part outer circulation logistics: by from ring coal gas processing part to gas making part mobile recycle stream.
In order to describe coal carbonization device charring furnace combustion chamber technological process, the present invention divides the whole feed gas constituents in combustion chamber according to fuel, oxygenant, three kinds of functions of temperature control agent, and, be defined as follows by virtual oxygen donator and virtual combustion gas body conceptual analysis combustion processes heat effect:
1. virtual oxygen donator is made of oxidant constituents and temperature control agent component, the oxygen components volumetric concentration can be controlled in the existing reliable rule of thumb data scope in the virtual oxygen donator: the ratio of first part's combustion chamber temperature control component volume amount and oxygen components volume amount is by 1.50～5.25 calculating (being that the oxygen components volumetric concentration is 16～40% in the virtual oxygen donator), and the present invention requires CO
2The temperature control component ratio of component is greater than the 0.50 poor nitrogenize with the realization combustion processes; Virtual oxygen donator temperature control agent component source is unrestricted: can from outside the gas maker or within, can be from gas making part internal recycle or outer circulation;
2. virtual combustion gas body is made of second section combustion chamber temperature control component and fuel element, and the calorific value of promptly virtual combustion gas body can be controlled in the existing reliable rule of thumb data scope: virtual combustion gas body volume calorific value is 1400～2600KCAL/NM
3, the component component of virtual combustion gas body source is unrestricted: can from outside the gas maker or within, can be from gas making part internal recycle or outer circulation.
In order to describe coal carbonization device charring furnace coking chamber technological process, the present invention divides the whole feed gas constituents of coking chamber according to fuel, oxygenant, three kinds of functions of coking chamber heat-carrying component, and presses heat-carrying process and the combustion processes that this conceptual analysis coking chamber takes place.Why do not use temperature control agent one speech, be to have much because of controlling factor in the coking chamber combustion processes, comprise: the temperature of the hot charcoal of space, place caloradiance, contact, a large amount of coking chamber heat-carrying component are to dissemination, the flame propagation velocity of " fuel and oxygenant ", exist many factors such as regional gas flow pattern at charcoal piece (or coal cinder), and " coking chamber fuel gas combustion processes " is the fuel gas combustion processes that there are significant difference in and " combustion chamber fuel gas combustion processes ".In some charring process technology, arranging coking chamber that certain fuel gas combustion reactions takes place (is to contain certain oxygenant O in the first via gas
2Component).
So far, this paper gaseous constituent that will go out, go into charring furnace ST is divided by following function or attribute:
1. combustion components, its definition from the charring furnace outside, enter the component combustion chamber, that participate in combustion reactions, the fuel element (H that consumes as combustion processes
2, CO, hydro carbons, H
2S) and oxidant constituents O
2After combustion processes finishes, partly or entirely combustion components is converted into flue gas, the residual combustion components that unburn transforms belongs to the superfluous combustion components of combustion processes, be that the combustion components amount comprises combustion components consumption and combustion components excess quantity, superfluous combustion components can be fuel gas or oxygenant gas, when the combustion components of surplus is oxygenant gas, usually be converted into flue gas in charring furnace charing section by reaction, i.e. may there be corresponding oxygen consumption reaction (the charring furnace local space may form combustion reactions) in charring furnace charing section;
Combustion components is divided into fuel element (H
2, CO, hydro carbons, hydrogen sulfide) and oxidant constituents O
2
2. combustion chamber temperature control component, its definition from the charring furnace outside, that in the combustion chambers burn process, exist, that possess control combustion product gases temperature function, but do not participate in the non-combustibleconstituents of combustion reactions, normally pass the combustion chamber and pass the non-combustibleconstituents component that coking chamber contacts with coal or charcoal, can be CO
2, N
2, Ar, H
2O etc.; Can be the logistics of gas making part internal recycle, can be gas making part outer circulation logistics, also can be the N that the external non-combustibleconstituents of input coal carbonization device carries such as air
2, external CO
2Deng;
Combustion chamber of the present invention is a generalized concept: fuel gas enters charring furnace and " charcoal or coal contact " with oxygenant generation combustion reactions gained flue gas, and its combustion space that " does not contact with charcoal or coal " promptly is combustion chamber of the present invention; Its form can be arbitrarily, but its flue-gas temperature must be by " combustion chamber temperature control component " control or major control;
3. coking chamber heat-carrying component (shift heat energy component), its definition from the charring furnace outside, pass coking chamber, that all contact with coal with charcoal, but do not participate in the component of combustion reactions, be commonly referred to as whole components (or its reformate gas) of first via gas;
Coking chamber heat-carrying component, flue gas composition (or its final products of combustion that does not comprise the second road gas, if the flue gas composition of the second road gas reacts in coking chamber generation secondary combustion, normally because combustion chamber oxygen surplus causes gas fume of combustion chamber to carry superfluous oxygen), do not comprise that the charcoal gaseous fraction of putting out that produces when water puts out charcoal does not belong to coking chamber heat-carrying component yet yet;
When the combustion components of combustion chamber surplus is oxygenant when (promptly having superfluous oxygen), the part of first via gas (normally small portion) is finished oxygen consumption reaction (the charring furnace local space may form combustion reactions) in charring furnace charing section and superfluous oxygen; In fact in existing charring process, there is the heat release combustion reactions of some amount in the charring furnace local space;
Usually say that during ordinary production, the circulation raw gas through coking chamber that does not participate in combustion reactions (not passing through the combustion chamber) belongs to coking chamber heat-carrying component (charring furnace heat-carrying component);
4. gasification component, its definition be by go into that the charring furnace coal charge carries or produce in processes such as the desorb of coking chamber internal cause coal charge, conversion, evaporation, cracking, coal gas generations, enter in the raw gas, but not with the component of combustion reactions, comprise coal cracked gaseous things such as water component that coal charge carries, constituent of air, tar steam usually, put out charcoal gas component;
5. other gaseous fraction comprises bleed sealing gland gas and other gas.The sealing gland of bleeding gas refer to when the charring furnace opening for feed and or discharge port etc. when using blanket gas, the part blanket gas enters charring furnace and finally enters the gas that bleeds in the raw gas;
6. dust;
7. burning transforms component.
Main research object component of the present invention is that preceding 3 compositions are combustion components, combustion chamber temperature control component and coking chamber heat-carrying component, the present invention is very little or almost not influence to the existing way influence of back four components, and supposition is to the not influence of existing way of back four components in the description of the invention process.
Core research object component of the present invention is that the 2nd component is combustion chamber temperature control component, and the present invention produces great effect to its existing way, and forms effect of the present invention based on this.
For coking chamber, pass coking chamber and coal with or the component that contacts of charcoal, the heat-carrying effect is all arranged, but the present invention uses notion to discuss problem in strict accordance with above-mentioned definition, prevents the chaos of conception.
The main ingredient of the flue gas of hydrocarbon fuel component and air perfect combustion is H
2O, CO
2, N
2, finally enter in ring coal gas, wherein H
2O very easily separates with other gas composition by cooling phase transformation condensation, and CO
2, N
2Then become awkward isolating flue gas composition, by contrast, N
2Then become the most difficult isolating flue gas composition.
Curiously, N
2But not products of combustion, but bring system into because of oxygen donator contains a large amount of nitrogen when introducing oxygenant.In other words, the nonnitrogenous gas of the oxygen donator of introducing or contain that easily separated temperature control component can reduce or thoroughly do away with the raw gas components system " have big quantity N
2The difficult separation performance that causes ".
Combustion chamber temperature control component, the component of candidate that conveniently obtains is: CO
2, N
2, H
2Totally three kinds of O.H wherein
2The physical sepn of O (condensation) and recycle process (vaporization, compression process) need a large amount of latent heats of vaporization and are difficult to recirculation because of formation contains tar sewage, therefore do not possess economy; N
2Be that we desire the alternate component; CO
2Be that the combustion chamber temperature control component that has existed (comprises CO in the common process raw gas
2, N
2, H
2Three combustion chambers of O temperature control component), it is from the burning conversion product of fuel element.
CO
2, N
2As combustion chamber temperature control component the macroscopic view contrast that raw gas components system PSA separation performance influences is seen Table 1.
Table 1 is " equivalent amount CO
2, N
2Sneak into CO
2-CH
4-CO-H
2System is told with PSA then again " contrast of the macroscopic view of gedanken experiment, the explanation of project comparative result:
1. CO is selected in first explanation for use
2As combustion chamber temperature control component, can reduce by 1 raw gas component number, this itself has just simplified the sepn process of raw gas;
When component was separated entirely, scheme one did not need to consider N
2Separate, scheme two must be considered CO
2Separate;
2. CO is selected in second explanation for use
2As combustion chamber temperature control component, extreme case can reduce the separating step number of raw gas component down: reduce several 1 time;
During such as production high performance fuel gas, need of scheme separate for 1 time, scheme two minimum 2 separation;
3. CO is selected in the 3rd explanation for use
2As combustion chamber temperature control component, sorbent material consumption much less (little, the less investment of equipment size), the adsorptive pressure that needs much lower (compression work is few, compressor less investment, the low less investment of system pressure, invalid compression work few) promptly reduces investment and cutting down the consumption of energy again; CO can be set
2Internal recycle;
4. CO is selected in the 4th explanation for use
2As combustion chamber temperature control component, its separate the back when discharging to active principle form to carry loss much smaller, can significantly improve the active principle rate of recovery;
5. CO is selected in the 5th explanation for use
2As combustion chamber temperature control component, it separates the active principle that carries when discharge the back is the fuel hydrocarbon gas and the hydrogen sulfide that need remove, and has purification methane (Sweet natural gas) effect and depriving hydrogen sulphide effect simultaneously; Select N for use
2As combustion chamber temperature control component, it separates the active principle that carries when discharge the back is low-calorie industrial chemicals H
2And CO, formation be that the high value component is carried loss, and be difficult to utilize.
Table 1 " equivalent amount CO
2, N
2Sneak into CO
2-CH
4-CO-H
2System
Tell again with PSA then " contrast of the macroscopic view of gedanken experiment
Sorbent material is to CO
2/ H
2The separation factor that component is right is much larger than to N
2/ H
2The separation factor that component is right can find out that about this point table 2 data are selected from the listed publication of table 3 from table 2 data.
Several sorbent materials of table 2 are to the separation factor of hydrogen
| Sorbent material | CO 2 | CO | CH 4 | N 2 | H 2 |
| Silica gel | 19.2 | 2.1 | 2.9 | 3.8 | 1 |
| Gac | 18.5 | 5.9 | 7.5 | 4.8 | 1 |
| The 5A molecular sieve | 54.5 | 18.3 | 9.8 | 7.2 | 1 |
| ? | ? | ? | ? | ? | ? |
| Sorbent material | CO 2 | CO | CH 4 | N 2 | H 2 |
| Silica gel | 5.05 | 0.55 | 0.76 | 1 | 0.26 |
| Gac | 3.85 | 1.23 | 1.56 | 1 | 0.21 |
| The 5A molecular sieve | 7.57 | 2.54 | 1.36 | 1 | 0.14 |
| ? | ? | ? | ? | ? | ? |
| Sorbent material | CO 2 | CO | CH 4 | N 2 | H2 |
| Silica gel | 6.62 | 0.72 | 1 | 1.31 | 0.34 |
| Gac | 2.47 | 0.79 | 1 | 0.64 | 0.13 |
| The 5A molecular sieve | 5.56 | 1.87 | 1 | 0.73 | 0.10 |
| ? | ? | ? | ? | ? | ? |
| Sorbent material | CO 2 | CO | CH 4 | N 2 | H 2 |
| Silica gel | 9.14 | 1 | 1.38 | 1.81 | 0.48 |
| Gac | 3.14 | 1 | 1.27 | 0.81 | 0.17 |
| The 5A molecular sieve | 2.98 | 1 | 0.54 | 0.39 | 0.05 |
| ? | ? | ? | ? | ? | ? |
| Sorbent material | CO 2 | CO | CH 4 | N 2 | H 2 |
| Silica gel | 1 | 0.11 | 0.15 | 0.20 | 0.05 |
| Gac | 1 | 0.32 | 0.41 | 0.26 | 0.05 |
| The 5A molecular sieve | 1 | 0.34 | 0.18 | 0.13 | 0.02 |
The publication of table 3 record table 2 data
Table 4 is that the sorbent material HXBC-15B of Huaxi Chemical Science and Technology Co Ltd, Chengdu contrasts the loading capacity data of different gaseous fractions under 38 ℃, as can be seen: under identical temperature and pressure, same sorbent material is different to the loading capacity of different gaseous fractions, and the quantity of adsorbents adsorb carbonic acid gas is much larger than the quantity of absorption nitrogen.
Sorbent material HXBC-15B to the absorption relative capacity data of several gaseous fractions relatively during table 438 ℃
More than analyze and point out: adopt CO
2Replace N
2As combustion chamber temperature control component under the precondition that keeps combustion chambers burn temperature controlled function (just stablizing the function of coking chamber temperature), can change raw gas forms, can under the prerequisite that is not changing existing charing device structure and operational condition (combustion product gases temperature, volumetric flow rate) substantially, realize the purpose of change raw gas system PSA separation characteristic, and this just the semicoke industry expect for many years and the integrated technique of the technical object of a kind of realization the " blue charcoal of low nitrogen oxygen-enriched combusting system and raw gas economic utilization thereof " do not found.Certainly, the present invention has also changed the first via gas (circulation thermophore raw gas) that passes coking chamber simultaneously and has formed, thereby has thoroughly changed the composition of charing workshop section logistics.
Table 5 has been listed CO
2, N
2Unit volume than dsc data, CO as can be seen
2Than N
2The unit volume specific heat of combustion much higher, that is to say that same heat-carrying capacity can reduce the heat-carrying gas volume amount, is beneficial to the reduction equipment size, reduce heat-carrying gas working cycle compression work and consume.Same in other words heat-carrying gas volume amount can increase the hot quantity of heat-carrying, can improve the heat that reclaims from hot charcoal logistics, improves the preheating temperature of coal charge, fuel saving gas consumption.
Table 5CO
2And N
2Perfect gas specific heat
Table 6 has been listed CO
2, N
2Thermal conductivity, as can be seen, at high temperature carbonization district CO more than 600 ℃
2Than N
2Thermal conductivity value be high, and the charing furnace gas mainly contacts by direct impact with the heat transfer of charcoal or coal and finishes equal-volume CO
2Than N
2Can quicken dry distillation of coal process, be beneficial to coal tar wet goods component and break away from the hot coal material.
Table 6 CO
2And N
2Thermal conductivity, kilocalorie/when rice (℃)
| Temperature, ℃ | N 2Thermal conductivity value | CO 2Thermal conductivity value | Ratio |
| 0 | 0.021 | 0.013 | 0.6190 |
| 100 | 0.030 | 0.020 | 0.6667 |
| 200 | 0.034 | 0.027 | 0.7941 |
| 400 | 0.043 | 0.041 | 0.9535 |
| 600 | 0.052 | 0.053 | 1.0192 |
| 800 | 0.057 | 0.065 | 1.1404 |
| 1000 | 0.063 | 0.074 | 1.1746 |
Again on the one hand, part or all of CO
2Thereby the heat-carrying component can reclaim available waste heat for the hot gas from other technological process reduces firing rate, such as using CO
2Heat-carrying component and high-temp waste gas heat exchange or directly utilize the high temperature high-purity CO
2Gas.
Again on the one hand, part or all of CO
2Thereby the heat-carrying component can reclaim available exhaust gas pressure energy for calming the anger from the band of other technological process, such as being high-purity CO from coal preparing natural gas process
2Band pressure venting.
In order to reduce the combustion processes hydrogen-consuming volume, can use low hydrogen content fuel gas, can reduce amount of moisture in the raw gas this moment, finally can reduce to contain the tar sewage quantity.
Therefore, technological thought of the present invention is, at N
2Be the conventional coal carbonization technology of combustion chamber main body temperature control component, with combustion chamber temperature control component N
2Partly or entirely change into CO
2, form with CO
2Coal carbonization technology (such as the blue charcoal technology of coal system) for (circulation) combustion processes main body temperature control component, under the prerequisite that does not change existing charing device structure and operational condition (combustion product gases temperature, volumetric flow rate) substantially, improvement is from ring coal gas separation performance, form the chemical industry type technology of production fine product: with coal, water, air is raw material, produces blue charcoal, tar, hydrogen, Sweet natural gas, CO
2Gas, sulphur can increase substantially resource value, increase substantially the handiness of regulating quality product, the remarkable stability that strengthens the control quality product simultaneously, cut down the consumption of energy.
The method of the invention is a kind of integrated technique technology, and its each detail section is mature technology, but the integrated artistic after the combination has produced aforesaid creative effect, thereby has novelty.
Core feature of the present invention is the products of combustion CO with non-oxidation agent effect, no combustion heat value
2Introduce the combustion chambers burn process, violate convention, seem to be absurdity, thereby show that the present invention is extremely unusual.
The method of the invention is not appeared in the newspapers.
Therefore, first purpose of the present invention is to propose a kind of with CO
2Oxygen enrichment coal carbonization technology for combustion processes main body temperature control component.
So second purpose of the present invention a kind of with CO
2Circulation gas is the oxygen enrichment coal carbonization technology of combustion processes main body temperature control component.
The 3rd purpose of the present invention is to propose a kind of with CO
2Coal system semicoke (blue charcoal) technology for combustion processes main body temperature control component can form with CO
2Circulation gas is the coal carbonization technology (such as the blue charcoal technology of coal system) of non-flammable heat-carrying component, under the prerequisite that does not change existing charing device structure and operational condition substantially, is raw material with coal, water, air, produces blue charcoal, tar, hydrogen, Sweet natural gas, CO
2Gas, sulphur, the chemical industry type technology of formation production fine product.
The 4th purpose of the present invention is to propose a kind of with CO
2Internal recycle gas is combustion processes main body temperature control component, with CH
4Outer circulation gas is coal system semicoke (blue charcoal) technology of combustion processes main fuel component, under the prerequisite that does not change existing charing device structure and operational condition substantially, form the two circulation chemical industry type technologies of hydrogen yield maximization of production fine product, with coal, water, air is raw material, produces blue charcoal, tar, hydrogen, Sweet natural gas, CO
2Gas, sulphur form the gas maker of maximum volume production hydrogen, significantly reduce simultaneously to contain the tar sewage quantity, save tar sewage burning process fuel consumption.
The 5th purpose of the present invention is to propose a kind of with CO
2Be the coal carbonization technology of combustion chamber temperature control component,, form the gas maker of producing hydrogen and Sweet natural gas by adjusting operation.
The 6th purpose of the present invention is to propose a kind of with CO
2Be the coal carbonization technology of combustion chamber temperature control component, can directly utilize other hot CO
2Gas reclaims its heat energy, fuel saving consumption, the output of raising product such as methane gas.
The 7th purpose of the present invention is to propose a kind of with CO
2Be the coal carbonization technology of combustion chamber temperature control component, be suitable for as system methanol feedstock gas from ring coal gas.
The 8th purpose of the present invention is to propose a kind of with CO
2For the coal carbonization of combustion chamber temperature control component with from ring coal gas system methyl alcohol integrated technique.
The result that the present invention pursues is: high flexibility of operation, high operational stability, high component yield, low energy consumption, low construction investment.
Summary of the invention
A kind of with CO
2Coal carbonization technology for combustion processes temperature control component is characterized in that comprising following steps:
1. gas making partly comprises charring furnace and coking chamber heat-carrying component internal circulation system, and charring furnace comprises the combustion chamber of fuel gas and the coking chamber of coal;
In coking chamber, according to the advance route of coal charge, being divided into first section is that coal preheating section (or claim gas cooling section), second section are that coal carbonization section, the 3rd section are charcoal cooling section (or claiming gas preheating section); In the 3rd section zone, comprise the first via gas of coking chamber heat-carrying component and two sections process material contact heat-exchangings and reclaim and become three sections process gas after its heat heats up, three sections process material leave three sections zones; In second section zone, gas fume of combustion chamber, three sections process gas carry out gas-solid with one section process material and directly contact generation charing effect, and two sections process material leave second section zone and enter the 3rd section zone, and two sections process gas leave second section zone and enter first section zone; In first section zone, after transmitting the heat cooling and sneak into one section generation gas with the outside certainly coal charge Contact Heating coal charge that adds, two sections process gas become one section product gas (raw gas), and become one section process material after coal charge heats up and enter second section zone;
At least a portion is returned coking chamber as coking chamber heat-carrying component based on the logistics of raw gas, constitutes gas making part coking chamber heat-carrying component internal recycle;
Gas making part coal gas product is as leaving the gas making part from ring coal gas;
It is characterized in that: the combustion chamber oxygen donator is oxygen enrichment or pure oxygen, with CO
2Be main combustion chamber temperature control component;
The definition of combustion chamber temperature control component is: from the charring furnace outside, the coexistence of combustion chamber and fuel element, possess the control combustion product gases temperature function, that do not participate in combustion reactions, pass the combustion chamber and pass that coking chamber contacts with coal charge, enter the non-combustibleconstituents in the raw gas when leaving charring furnace.
Combustion chamber CO
2The temperature control component ratio of component usually greater than 0.50, generally greater than 0.85 more preferably greater than 0.95.The definition of combustion chamber temperature control component ratio is: the ratio of specific combustion chamber temperature control component volume and whole combustion chambers temperature control component volume.5, method according to claim 2 is characterized in that:
Combustion chamber CO
2The temperature control component ratio of component, make the combustion chambers burn flue-gas temperature finally satisfy coking chamber charing section temperature index: lump coal is heated to by this section and is generally 600～850 ℃, is generally 750～850 ℃, is preferably 780～820 ℃ temperature.
Combustion chamber CO
2The temperature control component ratio of component, to make the combustion chambers burn flue-gas temperature be generally 600～900 ℃, be generally be 700～900 ℃, be preferably 750～850 ℃.
The whole feeding gas in combustion chamber of the present invention satisfy following regulation usually: the whole feeding gas in combustion chamber are divided into virtual oxygen donator and virtual fuel body; Virtual oxygen donator is by oxygen components and the CO of first part
2Component constitutes, the CO of first part
2The ratio of component volume amount and oxygen components volume amount calculates (being that the oxygen components volumetric concentration is 16～40% in the virtual oxygen donator), CO by 1.50～5.25
2The temperature control component ratio of component is greater than 0.50; Virtual fuel body volume calorific value is 1400～2600KCAL/Nm
3
The whole feeding gas in combustion chamber of the present invention satisfy following general provision: virtual oxygen donator is by oxygen components and the CO of first part
2Component constitutes, the CO of first part
2The ratio of component volume amount and oxygen components volume amount calculates (being that the oxygen components volumetric concentration is 21～35% in the virtual oxygen donator), CO by 1.85～3.76
2The temperature control component ratio of component is greater than 0.90; Virtual fuel body volume calorific value is 1700～2400KCAL/Nm
3
The present invention produces low CO
2During coal gas, it is characterized in that: 1. in the gas making part, raw gas enters transformation fractionation by adsorption part PSA1008 after at least a portion de-oiling from ring, and during absorption working condition, raw gas passes when adsorbent bed after the de-oiling, sorbent material selective adsorption CO
2And the easier component that is adsorbed, H
2, CH
4, component such as CO passes adsorbent bed becoming and takes off CO
2Coal gas; At least a portion is taken off CO
2Coal gas returns the charring furnace coking chamber as coking chamber heat-carrying component, forms coking chamber heat-carrying component internal recycle gas; During the desorb operating mode, obtain rich CO
2Gas, the rich CO of at least a portion
2Gas returns the charring furnace combustion chamber combustion chamber temperature control component is provided, and forms combustion chamber temperature control component internal recycle gas; Do not return the coal gas (raw gas and or take off CO of charring furnace in gas making part
2Coal gas) be used as from ring coal gas.
The present invention in the gas making part, isolates rich CO based on the logistics employing variable-pressure adsorption separating method of de-oiling raw gas
2Gas, the rich CO of at least a portion
2Gas returns the charring furnace combustion chamber combustion chamber temperature control component is provided, and forms combustion chamber temperature control component internal recycle gas.
The present invention in the gas making part, adopts variable-pressure adsorption separating method to isolate based on the logistics of de-oiling raw gas and takes off CO
2Coal gas, at least a portion is taken off CO
2Coal gas returns the charring furnace coking chamber coking chamber heat-carrying component is provided, and forms coking chamber heat-carrying component internal recycle gas.
The present invention from ring coal gas processing part, adopts variable-pressure adsorption separating method to isolate rich CO based on the logistics from ring coal gas
2Gas WH, at least a portion WH return the charring furnace combustion chamber and make combustion chamber temperature control component, form combustion chamber temperature control component outer circulation gas.
The present invention from ring coal gas processing part, adopts variable-pressure adsorption separating method to isolate poor H based on the logistics from ring coal gas
2, poor CO
2Gas returns the charring furnace combustion chamber combustion chamber fuel element is provided, and forms combustion chamber fuel element outer circulation gas.
The present invention forms when producing high performance fuel gas technology, and it is characterized in that: 1. in the gas making part, raw gas enters transformation fractionation by adsorption part PSA1008 after the de-oiling, during absorption working condition, after the de-oiling raw gas pass adsorbent bed, sorbent material selective adsorption CO
2And the easier component that is adsorbed, H
2, CH
4, component such as CO passes the adsorbent bed high heating value gas that becomes, a part of high heating value gas returns the charring furnace coking chamber, as coking chamber heat-carrying component, forms coking chamber heat-carrying component internal recycle gas.The operational condition of transformation fractionation by adsorption separate part PSA1008 is generally: adsorption process pressure is between 0.13～0.5MPa (absolute pressure); During the drop pressure end of processing, adsorption column pressure is between 0.07～0.13MPa (absolute pressure); The reverse step that vacuumizes is when finishing, and adsorption column pressure is between 0.003～0.03MPa (absolute pressure); Adsorbent bedly constitute layering combination cot, the CO of purified gas for a kind of in the activated alumina, gac, silica gel or by wherein several
2Volumetric concentration is less than 15%, and stripping gas carbonic acid gas volumetric concentration is greater than 90%.The operational condition preferably of transformation fractionation by adsorption separate part PSA1008 is: adsorption process pressure is between 0.15～0.3MPa (absolute pressure); Adsorbent bed is the layering combination cot that activated alumina, silica gel constitute, the CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%.Transformation fractionation by adsorption part PSA1008, partly or entirely stripping gas returns the charring furnace combustion chamber, and combustion chamber temperature control component is provided, and forms combustion chamber temperature control component internal recycle gas.
The present invention forms first kind when ring gas production hydrogen and fuel gas technology, it is characterized in that: 2. comprise hydrogen purification part PSA2089 from ring coal gas processing part; In the PSA2089 part, during absorption working condition, unstripped gas passes when adsorbent bed, and sorbent material selective adsorption non-hydrogen components, hydrogen component are passed the adsorbent bed PSA2089 of becoming purified gas, and the PSA2089 stripping gas is as fuel gas.The operational condition of PSA2089 is generally: adsorption process pressure is between 0.5～2.5MPa (absolute pressure); During the drop pressure end of processing, adsorption column pressure is between 0.25～0.40MPa (absolute pressure); When reverse deflation course finished, adsorption column pressure was between 0.13～0.15MPa (absolute pressure); Adsorbent bedly constitute layering combination cot, the H of purified gas for a kind of in the gac, silica gel, zeolite molecular sieve or by wherein several
2Volumetric concentration is greater than 95%, H
2The volume yield is greater than 92%.The operational condition of PSA2089 is generally: adsorption process pressure is between 0.6～1.5MPa (absolute pressure); The reverse VC step that vacuumizes is when finishing, and adsorption column pressure is between 0.02～0.05MPa (absolute pressure); The H of purified gas
2Volumetric concentration is greater than 99%, H
2The volume yield is greater than 90%.
The present invention forms second kind when ring gas production hydrogen and fuel gas technology, it is characterized in that: 2. comprise from ring coal gas processing part and take off CO
2Part PSA2008 and hydrogen purification part PSA2009; In the PSA2008 part, during absorption working condition, unstripped gas passes when adsorbent bed, sorbent material selective adsorption CO
2And the easier component that is adsorbed, H
2, CH
4, component such as CO passes the adsorbent bed PSA2008 of becoming purified gas, at least a portion PSA2008 stripping gas returns the charring furnace combustion chamber, and combustion chamber temperature control component is provided, and forms combustion chamber temperature control component outer circulation gas; In the PSA2009 part, during absorption working condition, unstripped gas passes when adsorbent bed, and sorbent material selective adsorption non-hydrogen components, hydrogen component are passed the adsorbent bed PSA2009 of becoming purified gas, and the PSA2009 stripping gas is as high methane gas.Take off CO
2The operational condition of part PSA2008 is generally: adsorption process pressure is between 0.2～0.8MPa (absolute pressure); During the drop pressure end of processing, adsorption column pressure is between 0.07～0.13MPa (absolute pressure); The reverse VC step that vacuumizes is when finishing, and adsorption column pressure is between 0.003～0.03MPa (absolute pressure); Adsorbent bedly constitute layering combination cot, the CO of purified gas for a kind of in the activated alumina, gac, silica gel or by wherein several
2Volumetric concentration is less than 15%, and stripping gas carbonic acid gas volumetric concentration is greater than 90%.The operational condition of hydrogen purification part PSA2009 is generally: adsorption process pressure is between 0.5～2.5MPa (absolute pressure); During the drop pressure end of processing, adsorption column pressure is between 0.25～0.40MPa (absolute pressure); When reverse deflation course finished, adsorption column pressure was between 0.13～0.15MPa (absolute pressure); Adsorbent bedly constitute layering combination cot, the H of purified gas for a kind of in the gac, silica gel, zeolite molecular sieve or by wherein several
2Volumetric concentration is greater than 95%, H
2The volume yield is greater than 90%.
The present invention forms the third when ring gas production hydrogen and fuel gas technology, it is characterized in that: 2. comprise carbon monodixe conversion part 2100 from ring coal gas processing part and take off CO
2Part PSA2008 and hydrogen purification part PSA2009; Carbon monodixe conversion hydrogen manufacturing part 2100 operational conditions are generally: the carbon monoxide transformation efficiency greater than 85%, oxygen all transforms, the organosulfur transformation efficiency is greater than 85%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.8MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that the molecular ratio of 300～2500 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide is 1.3～6.0 that average reaction temperature is lower than 350 ℃, pressure; Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA2008; Take off CO
2The operational condition of part PSA2008 is generally: adsorption process pressure is between 0.2～0.7MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%.The operational condition of hydrogen purification part PSA2009 is generally: adsorption process pressure is between 0.6～1.5MPa (absolute pressure); The reverse VC step that vacuumizes is when finishing, and adsorption column pressure is between 0.02～0.05MPa (absolute pressure); The H of purified gas
2Volumetric concentration is greater than 99%, H
2The volume yield is greater than 94%.Carbon monodixe conversion hydrogen manufacturing part 2100 operational conditions are generally: the carbon monoxide transformation efficiency greater than 90%, oxygen all transforms, the organosulfur transformation efficiency is greater than 90%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.6MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that 500～2000 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide molecule ratio are 1.5～4.5 that average reaction temperature is lower than 300 ℃, pressure; Enter after conversion gas reduction temperature to the 35～45 ℃ dehydration and take off CO
2Part PSA2008; Take off CO
2The operational condition of part PSA2008 is generally: adsorption process pressure is between 0.2～0.5MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%.The operational condition of hydrogen purification part PSA2009 is generally: adsorption process pressure is between 0.7～1.2MPa (absolute pressure); The H of purified gas
2Volumetric concentration is greater than 99%, H
2The volume yield is greater than 96%.Carbon monodixe conversion hydrogen manufacturing part 2100 operational condition preferablies are: the carbon monoxide transformation efficiency greater than 95%, oxygen all transforms, the organosulfur transformation efficiency is greater than 95%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.5MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that 800～1500 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide molecule ratio are 1.5～3.5 that average reaction temperature is lower than 250 ℃, pressure; Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA2008; The operational condition of transformation fractionation by adsorption separate part PSA2008 preferable be: adsorption process pressure is between 0.15～0.4MPa (absolute pressure); Adsorbent bed is that activated alumina, silica gel constitute layering combination cot, the CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%.
The present invention forms when ring coal gas main product hydrogen technology, and it is characterized in that: 2. at hydrogen purification part PSA2009, partly or entirely the PSA2009 stripping gas returns the charring furnace combustion chamber, and the combustion chamber fuel element is provided, and forms combustion chamber fuel element outer circulation gas.
The invention provides combustion chamber temperature control component CO
2Logistics can be used as the heat-obtaining body, provide combustion chamber temperature control component CO such as at least a portion
2Logistics and the high-temperature flue gas heat exchange of boiler after the hot gas of gained enter the combustion chamber, perhaps provide combustion chamber temperature control component CO such as at least a portion
2Logistics and the heat exchange of sulfur recovery facility high-temperature tail gas after the hot gas of gained enter the combustion chamber.
The invention provides combustion chamber temperature control component CO
2Logistics can be technology with pressure discharging gas, provide combustion chamber temperature control component CO such as at least a portion
2Logistics be discharging gas from coal preparing natural gas process.
The present invention forms when ring coal gas system methanol feedstock gas technology, it is characterized in that: 1. from ring coal gas processing part, at least a portion from ring coal gas as making methanol feedstock gas.
The present invention forms first kind when ring coal gas system methanol feedstock gas technology, and common operational condition is: 2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.0～2.5.Comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.5～2.0; Carbon monodixe conversion hydrogen manufacturing part 3100 operational conditions are: the carbon monoxide transformation efficiency is regulated conversion gas H
2/ CO molecular ratio is 1.5～2.5, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that the molecular ratio of 3.0～15MPa (absolute pressure), water vapor/carbon monoxide is 0.7～2.5 that average reaction temperature is lower than 350 ℃, pressure; The hot conversion gas that leaves shift-converter enters methanol sythesis reactor.
The present invention forms first kind when ring coal gas system methanol feedstock gas technology, and general operational condition is: 2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.5～2.0; Carbon monodixe conversion hydrogen manufacturing part 3100 operational conditions are: the carbon monoxide transformation efficiency is regulated conversion gas H
2/ CO molecular ratio is 1.5～2.5, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that the molecular ratio of 3.0～15MPa (absolute pressure), water vapor/carbon monoxide is 0.7～2.5 that average reaction temperature is lower than 350 ℃, pressure; The hot conversion gas that leaves shift-converter enters in the circulation gas raw material of methanol sythesis reactor.
The present invention forms first kind when ring coal gas system methanol feedstock gas technology, and preferable operational condition is: 2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.5～2.0; Take off the impurity step from ring coal gas through hydrogenation, organosulfur is converted into hydrogen sulfide, oxygen is converted into water, reforming gas is divided into two-way, and first via reforming gas obtains conversion gas, the H of the gas mixture of the conversion gas and the second road reforming gas through carbon monodixe conversion part 3100
2/ CO molecular ratio is 1.5～2.0.
The present invention forms first kind when ring coal gas system methanol feedstock gas technology, the operational condition of carbon monodixe conversion part 3100 normally: 2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is adjusting conversion gas H
2/ CO molecular ratio is 1.5～2.0; Carbon monodixe conversion hydrogen manufacturing part 3100 operational conditions are: the carbon monoxide transformation efficiency greater than 50%, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that the molecular ratio of 3.0～15MPa (absolute pressure), water vapor/carbon monoxide is 0.7～2.5 that average reaction temperature is lower than 350 ℃, pressure.
The present invention forms first kind when ring coal gas system methanol feedstock gas technology, the operational condition of carbon monodixe conversion part 3100 generally is: 2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, carbon monodixe conversion hydrogen manufacturing part 2100 operational conditions are: the carbon monoxide transformation efficiency is greater than 65%.
The present invention forms first kind when ring coal gas system methanol feedstock gas technology, the operational condition preferably of carbon monodixe conversion part 3100 is: 2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, carbon monodixe conversion hydrogen manufacturing part 2100 operational conditions are: the carbon monoxide transformation efficiency is greater than 85%.
The present invention forms second kind when ring coal gas system methanol feedstock gas technology, operational condition normally: 2. comprise carbon monodixe conversion part 4100 from ring coal gas processing part, its function is adjusting conversion gas H
2/ CO molecular ratio is 1.5～2.0; Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA4108, PSA4108 takes off CO
2Gas is as system methanol feedstock gas;
The present invention forms second kind when ring coal gas system methanol feedstock gas technology, and operational condition generally is: 2. comprise carbon monodixe conversion part 4100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.5～2.0; Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA4108, PSA4108 takes off CO
2Gas is as system methanol feedstock gas; Carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: the carbon monoxide transformation efficiency is regulated conversion gas H
2/ CO molecular ratio is 1.5～2.0, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.8MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that the molecular ratio of 300～2500 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide is 0.7～2.0 that average reaction temperature is lower than 350 ℃, pressure; Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.2～0.7MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%.
The present invention forms second kind when ring coal gas system methanol feedstock gas technology, operational condition preferable be: 2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: carbon monoxide transformation catalyst bed working pressure is 0.3～0.6MPa (absolute pressure); Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.2～0.5MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%.
The present invention forms second kind when ring coal gas system methanol feedstock gas technology, and operational condition is preferably: 2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: carbon monoxide transformation catalyst bed working pressure is 0.3～0.5MPa (absolute pressure); Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.15～0.4MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%; Adsorbent bed is that activated alumina, silica gel constitute the layering combination cot.
The present invention forms the third when ring coal gas system methanol feedstock gas technology, operational condition is generally: 2. comprise carbon monodixe conversion part 4100 from ring coal gas processing part, take off the impurity step from ring coal gas through hydrogenation, organosulfur is converted into hydrogen sulfide, oxygen is converted into water, reforming gas is divided into two-way, first via reforming gas obtains conversion gas, the H of the gas mixture of the conversion gas and the second road reforming gas through carbon monodixe conversion part 4100
2/ CO molecular ratio is 1.5～2.0; Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA4108, PSA4108 takes off CO
2Gas is as system methanol feedstock gas;
The present invention forms the third when ring coal gas system methanol feedstock gas technology, and operational condition is generally: 2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: the carbon monoxide transformation efficiency is regulated conversion gas H
2/ CO molecular ratio is 1.5～2.0, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.8MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that the molecular ratio of 300～2500 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide is 0.7～2.0 that average reaction temperature is lower than 350 ℃, pressure; Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.2～0.7MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%.
The present invention forms the third when ring coal gas system methanol feedstock gas technology, operational condition preferable be: 2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: carbon monoxide transformation catalyst bed working pressure is 0.3～0.6MPa (absolute pressure); Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.2～0.5MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%.
The present invention forms the third when ring coal gas system methanol feedstock gas technology, and operational condition is preferably: 2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: carbon monoxide transformation catalyst bed working pressure is 0.3～0.5MPa (absolute pressure); Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.15～0.4MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%; Adsorbent bed is that activated alumina, silica gel constitute the layering combination cot.
The present invention forms when ring coal gas system methyl alcohol integrated technique and is characterised in that: 2. comprise carbon monodixe conversion part 5100, methane steam transform portion 5200, synthesizing methanol part 5300 from ring coal gas processing part, the hot conversion gas that leaves shift-converter enters the methane steam conversion process and obtains pyrolytic conversion gas, and reforming gas directly enters methanol synthesis reactor with suitable high state of temperature or enters in the methanol synthesis reactor charging.
Embodiment
Below describe the present invention in detail.
Pressure of the present invention refers to absolute pressure.
Gas component concentrations of the present invention when not specializing, is volumetric concentration.
This paper is the process modification of example explanation the present invention to the blue charcoal device of internal heat type with the blue charcoal device technique of large-scale upright furnace (600,000 t/a upright furnace) of Anshan Research Inst. of Heat Energy, China Iron ﹠ Steel Group and Huang gang, Hubei metallurgical furnace limited liability company of Huaxing.Yet this can not limit Application Areas of the present invention.
This section technical process that is used to describe common process " carbonization process and charring furnace thermophore cyclic part " (or being referred to as the gas making part).At first pack in the coal groove of furnace roof topmost by being equipped with qualified shove charge coal that coal workshop section ships, pack in the coking chamber through putting coal cock and auxiliary coal bin again.Continuously to the coking chamber coal.The lump coal that adds coking chamber moves from top to bottom, sends into the high-temperature gas counter current contact of coking chamber with the combustion chamber.The top of coking chamber is preheating section, and lump coal is heated to about 350 ℃ in this section; Lump coal continues to move down the retort section that enters coking chamber middle part, and lump coal is heated to 780～820 ℃ by this section, and is blue charcoal by charing; When blue charcoal passes through the cooling section of coking chamber bottom, being passed into this section thermophore circulating gas is cooled to 180～250 ℃ and becomes warm charcoal, the temperature charcoal enters and puts out charcoal section (quenching section) and be cooled to about 80 ℃ by coke quenching water, after discharging continuously with the put-focus machine of scraper plate, falls on the dryer by chute.The gas mixture (raw gas) of the coal gas that the coal gas that coal charge produces in carbonization process, combustion chamber produce when entering the high-temp waste gas of coking chamber and cooling coke, enter pneumatic trough through upcast, bridge tube, the gas mixture about 150～200 ℃ (raw gas) is cooled to about 80 ℃ through the cyclic ammonia water sprinkling in bridge tube and pneumatic trough.The ammonia water and tar oil that cooled coal gas gets off with condensation through air suction pipe enters gas purification workshop section.The coal gas of upright furnace heating usefulness is through the further cooling of gas purification workshop section and the coal gas after purifying.The air of upright furnace heating usefulness is supplied with by air-blaster pressurization back, coal gas and air mix through burner, in horizontal quirk internal combustion, and the high-temp waste gas that burning produces, enter coking chamber by equally distributed air inlet port on the coking chamber side wall, utilize the heat of high-temp waste gas that coal charge is carried out charing.The raw gas that comes out from upright furnace, effuser be recycled ammoniacal liquor spray be cooled to 80～90 ℃ after, enter washing tower along inhaling gas pipe through gas-liquid separator; Ammoniacal liquor is by washing tower top spray, and the ammoniacal liquor that the bottom has tar enters heat ring tank; Coal gas is entered by direct-cooled washing tower bottom, and top is discharged and entered inter cooler; Coal gas is cooled to 40～45 ℃ by 80 ℃.Coal gas enters the Root's blower pressurization behind straight a, water cooler, use as purifying coal gas behind electrical tar precipitator.In common process, a large amount of raw gas are directly sent upright furnace combustion chamber, sewage burning etc. back to and are acted as a fuel.From the tar ammonia that gas-liquid separator and direct-cooled washing tower come out, flow into heat ring tank standing separation tar certainly, tar dewaters with being pumped to the tar storage tank, and thermal cycling ammoniacal liquor is with being pumped to the furnace roof effuser and direct-cooled washing tower recycles.From the tar ammonia that inter cooler comes out, flow into cold ring tank standing separation tar certainly, tar is with being pumped to the dehydration of tar storage tank, and cold cyclic ammonia water recycles with being pumped to inter cooler.Tar (moisture＜4%) after the dehydration of tar storage tank is delivered to tar job shop or entrucking outward transport.
According to common process, a large amount of raw gas are directly done fuel, the significant wastage that causes hydrogen to be worth.2580 kilocalories/standard cubic meter of hydrogen standard Lower heat value, 8589 kilocalories/mark of methane standard Lower heat value is 3.33 times of hydrogen standard calorific value, methane (with reference to the Sweet natural gas appraisal) 1.5～2.5 yuan/standard cubic meter of price, calorific value is of equal value to be calculated by waiting, hydrogen is worth only 0.45～0.75 yuan/standard cubic meter, and as industrial chemicals, 1.5～2.5 yuan/standard cubic meter of hydrogen worth up to, clearly, hydrogen is worth huge 1.05～1.75 yuan/standard cubic meter of waste.Because upright furnace should not be lower than 1700～1800 kilocalories/standard cubic meter with calorific value of fuel gas, and the absorption of common process conversion gas transformation is carried hydrogen tail gas calorific value between 1100～1350 kilocalories/standard cubic meter, can't use in a large number, have to use the high raw gas of hydrogen richness.And a function of the present invention is elimination or reduces blue charcoal device fuel raw gas quantity, reduces the hydrogen waste.Method is to make the stripping gas (hydrogen-depleted gas body) that the absorption of high heating value conversion gas transformation puies forward the hydrogen process to replace.The blue charcoal device of large-scale upright furnace (600,000 t/a upright furnace), common process, upright furnace heating " H in the firing tunnel in coking furnace
2+ CO * 95% " volumetric concentration about 40.3%; if burnt 11000 standard cubic meter/hour raw gas; be equivalent to burn 4000 standard cubic meter/hour hydrogen; hydrogen price and fuel price difference are calculated by 1.0 yuan/standard cubic meter; be worth differ 4000 yuan/time; annually calculated by 7920 hours, up to 3,168 hundred million yuan/year, price differential is huge.
Below describe gas wet depriving hydrogen sulphide of the present invention and solvent direct oxidation regeneration system sulphur combination process in detail.
The present invention may need to be used with gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration system sulphur combination process, described gas wet depriving hydrogen sulphide technology refers to: the depriving hydrogen sulphide solvent is the aqueous solution that contains solvent composition, and described solvent direct oxidation regeneration system sulphur refers to: directly contact at rich solvent and oxygen-containing gas (being generally air) and finish that hydrogen sulfide is converted into sulphur (such as foam sulphur) in the solvent composition regenerated while rich solvent.Described gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration system sulphur combination process have multiple, such as improvement anthraquinone disulphonate method (ADA method), titanium cobalt phthalocyanine monosulfonate doctor treatment (PDS method), " PDS+ tannin extract method " (tannin extract method), generally with the hydrogen sulfide in the absorption coal gas such as alkaline carbonic acid sodium, ammonia soln, it is big to have processing power, desulfurization and regeneration all can be carried out continuously, advantages such as labour intensity is little, simultaneously also can remove prussic acid removing hydrogen sulfide, generally be adopted by coke-oven plant both at home and abroad.At present, the most ripe with improvement anthraquinone disulphonate method (ADA method) and " PDS+ tannin extract method " (tannin extract method).
Improve anthraquinone disulphonate method (ADA method) desulfuration solution by 2 of interpolation equal proportion in the dilute sodium carbonate solution, 6-and 2, the sodium salt solution of 7-anthraquinone disulfonic acid (ADA) and some other components are formulated.Have that desulfuration efficiency height (can reach more than 99.5%), coal gas adaptability are strong, the temperature, pressure wide accommodation, doctor solution is nontoxic, equipment corrosion is little, byproduct sulphur quality advantages of higher.Obtained widespread use in the coke-oven plant.But there are shortcomings such as easy obstruction, ADA cost an arm and a leg in it.
The tannin extract method be on the basis of improvement ADA method, improve, a kind of more advanced coal gas desulfurization technology that researchdevelopment is got up, adopt tannin extract to replace ADA.The tannin extract method is an absorption liquid with ammoniacal liquor, is catalyzer with PDS and adds promotors such as tannin extract.PDS is a kind of polymkeric substance, and its main component is binuclear phthalocyanine cobalt six ammonium sulphonates, to H
2The S liquid phase oxidation reaction has high catalytic performance, and composition combined action such as PDS and promotor tannin extract can provide higher catalytic activity.The effect of promotor mainly is: make the easier complexing of oxygen, accelerate sulphur atom come off, have good clear tower effect.Tannin extract is to be the afforestation product of main raw material preparation with natural wild plant, and it is cheap, is 1/6 of ADA.Desulfurizing tanning extract is compared with improvement ADA method, all can compare favourably on the key technical indexes such as gas purification degree, solution sulfur capacity, sulfur recovery rate.Tannin extract method typical commercial application flow process is as follows: be introduced into tubulent contact tower bottom and cat head from the raw gas (pressure-fired) of the cold bulging worker of preceding operation workshop section and spray the doctor solution counter current contact of getting off, thereby the continuous turbulence of polypropylene pellets increases contact area in the tubulent contact tower, improve desulfuration efficiency, then series connection enters two tassement polaire thionizer bottoms and cat head and sprays the doctor solution counter current contact of getting off and absorb afterwards (the complete adverse current of doctor solution and coal gas), H in the coal gas successively
2S content can reach 0.02g/Nm
3Below, after removing droplet, mist workshop section delivers to follow-up worker workshop section through catching.From tubulent contact tower, absorbed H
2The doctor solution of S and HCN flows into the solution circulated groove, after replenishing strong aqua and catalyst solution, be pumped to the pressurized air that regenerator column (A) bottom and compressed air station send here and flow to into regenerating with solution circulated, regenerated liquid returns the tubulent contact tower top and sprays desulfurization from regenerator column top, so recycle; Go into thionizer (B) earlier from the desulfurization lean solution of regenerator column (B), absorbed H at this
2The doctor solution of S and HCN is gone into thionizer (A) after flowing to additional equally strong aqua of semi lean solution groove and catalyst solution after the semi-leanpump pressurization, absorbed H in thionizer (A)
2The doctor solution of S and HCN flow to the rich solution groove and pumps the pressurized air of sending here to regenerator column (B) and compressed air station with the rich solution pump and flow to into regenerating, and the lean solution after the regeneration is returned thionizer (B) top and sprayed desulfurization from tower top, so recycle.The sulphur foam that produces in the regenerator column then flows into the sulphur foam chute certainly by regenerator column top expansion section s, by sending into sulfur melting kettle after the pressurization of sulphur foam pump, produces sulphur and sells outward again.Tannin extract method process characteristic is as follows:
1. according to the different requirements of coal gas desulfurization hydrogen precision, determine the setting of depriving hydrogen sulphide mass transfer workshop section, can adopt Dan Ta, the series connection of two towers or three tower cascade connected absorption, but removal of organic sulfur from and inorganic sulfur and prussic acid, desulfuration and decyanation efficient height; Hydrogen sulfide content in the coal gas can be taken off to≤20 milligrams/standard cubic meter;
2. tower carrying out adopted in regeneration, and pressurized air is advertised, and oxidation regeneration speed is fast, guaranteed that the sulphur foamy generates and flotation process has enough strokes;
3. " PDS+ tannin extract " composite catalyst, the catalyst activity height, consumption is few, and is cheap in addition, can significantly reduce catalyst costs;
4. adopting the ammonia that self contains in the coal gas is alkali source, can reduce the outer alkali source quantity that supplies, and reduces production costs;
5. absorb with regeneration and all carry out at normal temperatures, technology is simple, and flow process is short, and equipment and materials is less demanding, and manufacturing expense is low;
6. sulfur recovery can directly be recovered as sulphur, and the sulphur foam separation is effective, is difficult for stopping up, and system is stable.
Because the tannin extract method possesses above-mentioned advantage, in the coal tar chemical industry journey project desulfurization process of design, majority adopts these technologies at present.Gas wet depriving hydrogen sulphide of the present invention and solvent direct oxidation regeneration system sulphur combination process are preferred method with the tannin extract method.
Based on purpose of the present invention, in order to guarantee the reactive behavior of sulfur-tolerant type carbon monoxide transformation catalyst, the hydrogen sulfide volumetric concentration in the reaction gas flow (conversion unstripped gas) must maintain a reasonable high level (should not be lower than 100PPm, usually above 200PPm, be higher than 300PPm especially).
Based on the present invention to from the ring coal gas take off CO
2Handle and form internal recycle CO
2The basic function of gas, the hydrogen sulfide volumetric concentration that the present invention will purify raw gas can be controlled at a higher range.
The hydrogen sulfide volumetric concentration that the present invention will purify raw gas is controlled at a higher range, makes the necessary mass transfer theory level of the depriving hydrogen sulphide mass transfer workshop section of gas wet hydrogen sulfide removal process less, adopts the series connection of single tower or two towers to absorb usually and gets final product.
The present invention is with rich CO
2Stripping gas (just rich hydrogen sulfide stripping gas simultaneously) is introduced upstream process and has been finished the depriving hydrogen sulphide that effluxes raw gas, has realized smart desulfurization in thick method depriving hydrogen sulphide step.
Below describe CO of the present invention in detail
2Outer circulation qi exhaustion hydrogen sulfide process DHS.
Hydrogen sulfide removal process DHS can adopt any feasible method.
CO
2A kind of method of outer circulation qi exhaustion hydrogen sulfide process DHS is, with CO
2The outer circulation pneumatic transmission is gone into blue charcoal stove combustion chamber, CO
2The hydrogen sulfide that circulation gas carries enters the gas-liquid mass transfer workshop section of raw gas hydrogen sulfide removal process, utilizes the raw gas hydrogen sulfide removal process to finish hydrogen sulfide and reclaims, simultaneously CO
2Components such as the carbon three that circulation gas carries, ethene act as a fuel to be utilized and to burn to be converted into and are easy to isolating H
2O and CO
2
CO
2The another kind of method of outer circulation qi exhaustion hydrogen sulfide process is to set up independently CO
2The solvent that circulation gas hydrogen sulfide removal process, raw gas hydrogen sulfide removal process use at first with CO
2Circulation gas contact back series connection enters the gas-liquid mass transfer workshop section of raw gas hydrogen sulfide removal process.
Can be directly from purify raw gas, extract hydrogen, but when extracting hydrogen to greatest extent and be target, adopt carbon monodixe conversion to make hydrogen usually, from conversion gas, extract hydrogen then.
According to from ring coal gas composition, temperature, pressure condition, from ring before coal gas becomes the carbon monodixe conversion reactor feed gas, may need through removing impurity (tar that may exist, naphthalene, dirt), increase water vapor concentration (satisfying the water charcoal molecular ratio of transformationreation needs), compression is boosted, a certain step or the Overall Steps of intensification, deoxygenation steps such as (catalytic hydrogenation deoxygenations).
Below describe in detail of the present invention from ring coal gas detar part 2105.
As required, the present invention is provided with from ring coal gas detar part 2105, owing in ring coal gas, contain impurity such as tar, in order to prolong the transformation catalyst life-span, improve the absorption of PSA transformation and put forward purposes such as hydrogen absorbent efficient, enter before the reactor of conversion process, from ring coal gas detar part 2105, to deviate to obtain detar from ring coal gas from the impurity such as tar in the ring coal gas, can adopt variable-pressure adsorption separating method, usually use impurity such as acticarbon tar adsorption, desorption method is a depressurization desorption, what heating desorption and flushing desorb combined method, rinsing gas can be come transformation into itself's gas transformation absorbed portion returns charring furnace stripping gas etc.
Enter the branch flow container and finish gas-liquid separation (liquid is oily(waste)water) such as boost to 0.3MPa (absolute pressure) from ring coal gas compressed machine, gas phase enters pretreater (being at least two) and removes components such as tar, and pretreated raw gas goes subsequent handling.The detar part is minimum to be made up of 2 pretreaters, and wherein one is in absorption de-oiling state, and another is in reproduced state or stand-by state.Preprocessing part uses acticarbon.For the hydrogen sulfide sectional pressure that guarantees that carbon monoxide transformation catalyst needs, it is adsorbent bed that most of hydrogen sulfide has passed detar part adsorption tower in the raw gas.
Below describe detar of the present invention in detail and enter humidification step 2106 from ring coal gas.
Enter humidification step 2106 in detar from ring coal gas, usually remove foreign material such as entrained oil dirt by grade one filter after, enter the conditioning tower bottom, in conditioning tower, finish water evaporation and add an amount of steam, after secondary filter removes the impurity such as liquid water, greasy dirt of deentrainment, become the conversion process unstripped gas then with the circulating hot water counter current contact.According to the working pressure needs, detar may need to pass through compressor boost before ring coal gas enters humidification step.
Below describe in detail of the present invention from ring coal gas carbon monodixe conversion hydrogen production process 2100.
Described carbon monodixe conversion hydrogen production process 2100 uses carbon monoxide transformation catalyst usually.Conversion process unstripped gas (behind the de-oiling humidification from ring coal gas) is finished the end reaction effluent that carbon monodixe conversion obtains, usually be cooled to 35～45 ℃ through condensation and finish gas-liquid separation, gained gas can be used as follow-up transformation absorbed portion unstripped gas, according to the difference from ring coal gas composition, carbon monodixe conversion rate, transformation is adsorbed the composition of unstripped gas and is changed within the specific limits.
From ring coal gas carbon monodixe conversion hydrogen production process 2100 operational conditions, should decide according to concrete unstripped gas composition, the catalyzer of selecting for use, concrete Action Target, its scope is very wide.
Be generally from ring coal gas carbon monodixe conversion hydrogen production process 2100 operational conditions: the carbon monoxide transformation efficiency greater than 85%, oxygen all transforms, the organosulfur transformation efficiency is greater than 85%; Carbon monoxide transformation catalyst bed operational condition is generally: it is that 0.2～2.5MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that the molecular ratio of 50～15000 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide is 1.3～6.0 that average reaction temperature is lower than 350 ℃, pressure; It is 30～50 ℃ that described transformation absorption unstripped gas temperature is generally.
Be generally from ring coal gas carbon monodixe conversion hydrogen production process 2100 operational conditions: the carbon monoxide transformation efficiency greater than 90%, oxygen all transforms, the organosulfur transformation efficiency is greater than 90%; Carbon monoxide transformation catalyst bed operational condition is generally: it is that 0.3～1.5MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that 150～5000 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide molecule ratio are 1.5～4.5 that average reaction temperature is lower than 300 ℃, pressure; Described transformation absorption unstripped gas temperature is generally 35～45 ℃.
Be preferably from ring coal gas carbon monodixe conversion hydrogen production process 2100 operational conditions: the carbon monoxide transformation efficiency greater than 95%, oxygen all transforms, the organosulfur transformation efficiency is greater than 95%; Carbon monoxide transformation catalyst bed operational condition is preferably: it is that 0.3～0.8MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that 450～1650 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide molecule ratio are 1.5～3.5 that average reaction temperature is lower than 250 ℃, pressure; Described transformation absorption unstripped gas temperature is preferably 35～45 ℃.
When internal recycle coal gas adopts the PSA technology to isolate combustion chamber temperature control component,, CO need be set according to the present invention
2Separate part PSA1008.
When ring coal gas adopts the hydrogen manufacturing of PSA technology,, can be provided with and take off CO according to the present invention
2Part 2008 and hydrogen purification part 2009 also can only be provided with hydrogen purification part 2089.
Below describe the sorbent material that transformation absorbed portion of the present invention uses in detail.
Absorption is meant: when the different materials contact of two kinds of phases, wherein the molecule of the low material of density at the higher material surface of density by the phenomenon of enrichment and process.Have adsorbing material (being generally the relatively large porosu solid of density) and be called as sorbent material, the material that is adsorbed (being generally less relatively gas of density or liquid) is called adsorbate.Absorption can be divided into four big classes by the difference of its character, that is: chemisorption, activated adsorption, kapillary is condensing and physical adsorption.Absorption in transformation absorption (PSA) gas separation unit is mainly physical adsorption.Physical adsorption is meant and relies on sorbent material and adsorption molecule CO
2Between the absorption carried out of molecular force (comprising Van der Waals force and electromagnetic force).Be characterized in: do not have chemical reaction in the adsorption process, what adsorption process was carried out is exceedingly fast, and the running balance between each the phase material that participates in adsorbing can be finished in moment, and this absorption is completely reversibility.Why the adsorption gas separating technology process is achieved is because two essential propertys that sorbent material is had in this physical adsorption: the one, to the adsorptive power difference of different components, the 2nd, the loading capacity of adsorbate on sorbent material rises with the dividing potential drop of adsorbate and increases, and descends with the rising of adsorption temp.Utilize first character of sorbent material, can realize the preferentially adsorbed of some component in the mixed gas and other component is purified; Utilize second character of sorbent material, can realize that sorbent material adsorbs under low temperature, high pressure and under high temperature, low pressure desorption and regeneration, thereby constitute the absorption and the reprocessing cycle of sorbent material, reach the purpose of continuous divided gas flow.The desorption method of transformation absorption sorbent material has depressurization desorption, heating desorption and flushing desorb and combination several different methods thereof.The sorbent material that the use of hydrogen process is proposed in described transformation absorption all is the solid particulate that has than bigger serface, mainly contains: activated alumina class, gac class and molecular sieve.The most important physical features of sorbent material comprises pore volume, pore size distribution, surface-area and surface properties etc.Different sorbent materials is owing to have different pore size distributions, different specific surface area and different surface propertieies, thereby each component in the mixed gas is had different adsorptive poweies and loading capacity.For the complicated unstripped gas F of composition, use multiple sorbent material in actual applications usually, press the absorption property compound adsorption bed of layering filling composition successively, to reach the separation purpose.Transformation is adsorbed under the situation of stable operation, and the sorbent material life-span is quite long, generally can reach 8～10 years even longer.Ability based on this absorption impurity composition that sorbent material had far is better than the characteristic of adsorbing the hydrogen ability, realizes the hydrogen purification among the unstripped gas F.Sorbent material is estimated the main adsorption isothermal line of measuring by experiment of the absorption property of gas, and good absorption property and bigger loading capacity are the primary conditions of superior adsorbent.Simultaneously, during industrial pressure-swing absorption apparatus selected adsorbent, must consider that sorbent material should be big as far as possible to the separation factor of each component.So-called separation factor is meant: when reaching adsorption equilibrium, and the ratio of (weak absorbed component is the residual volume/total amount of weak absorbed component in adsorption bed in the adsorption bed dead space) and (strong absorbed component is the residual volume/strong total amount of absorbed component in adsorption bed in the adsorption bed dead space).Separation factor is big more, and it is easy more to separate.Generally speaking, the sorbent material separation factor in the transformation absorption hydrogen purifying plant should not be less than 3.In addition, in industrial pressure-swing adsorption process, also should consider contradiction between adsorption and desorption.Generally speaking, the easy more then desorb of absorption is difficult more.As to strong adsorbates such as hydrogen sulfide, should select more weak relatively sorbent material of adsorptive power such as silica gel etc., desorb is easier to so that loading capacity is suitable; And to N
2, O
2, weak adsorbate such as CO, just should select stronger relatively sorbent material of adsorptive power such as molecular sieve, CO special use sorbent material etc., so that loading capacity is bigger, separation factor is higher.In addition, in adsorption process, because the adsorption bed internal pressure is constantly to change, thereby sorbent material also should have enough intensity and resistance to abrasion.
In several sorbent materials that the transformation absorbed portion is used always, high-voidage activated alumina (Al
2O
3) belong to the solid that water is had strong avidity, general heat dehydration or the preparation of thermal activation method of adopting aluminum trihydrate or gibbsite, physical and chemical performance is extremely stable, resistance to wear, resist broken, nontoxic, mainly be seated in the bottom of adsorption tower, adsorb the moisture among the unstripped gas F, be used for the drying of gas, prevent that other sorbent materials suction back adsorptive poweies from reducing.The silica type sorbent material, be mainly used in and remove water, hydrogen sulfide, carbonic acid gas, heavy hydrocarbon etc., silica gel has high separation factor to the hydrogen sulfide in hydrogen sulfide, carbonic acid gas, methane, the nitrogen system, and silica gel particularly Kiselgel A has high separation factor to the carbonic acid gas in carbonic acid gas, methane, the nitrogen system.Gac class sorbent material is to be the flourishing especially special-purpose activated charcoal of hole that raw material obtains through chemical especially and thermal treatment with the coal, belong to the nonpolarity sorbent material of water-resisting type, be characterized in the oxide-base that had of surface because of and inorganics impurity make surface properties show as low-pole or nonpolarity, add the king-sized internal surface area that gac has, make gac become a kind of superior adsorbent that can adsorb multiple low-pole and nonpolar organic molecule in a large number, usually fill in the middle part of adsorption tower, be mainly used in the carbonic acid gas and the part methane that remove with the hydrogen coexistence, since cheap and loading capacity is bigger, be a kind of sorbent material commonly used of a large amount of uses.Zeolite molecular sieve class sorbent material is a kind of inclined to one side silico-aluminate of crystal form that has the cubes skeleton structure, contains alkaline earth element, belong to strong polar adsorbent, very consistent aperture structure and extremely strong adsorption selectivity are arranged, usually fill in the top of adsorption tower, be mainly used in the nitrogen, carbon monoxide and the methane that remove with the hydrogen coexistence.
Below describe the programstep order of the adsorption tower of transformation absorbed portion use of the present invention in detail.
Transformation absorbed portion of the present invention, the number of every group of adsorption tower be 2～24 or etc. many, the tower number that is in adsorbed state simultaneously can be two or more.All transformation absorbed portions, every adsorption tower all moves in proper order by the programstep of its place group, just staggers mutually on the time.The adsorption tower of each workshop section be in the tower number of adsorbed state can be identical also can be inequality.The increase and decrease of tower number all presses number of times to change, and what of isolation step can be determined according to the concrete operations needs.
Below describe transformation absorbed portion concrete operation method of the present invention in detail.
The transformation adsorption separation process of coal gas described herein and conversion gas thereof belongs to coal gas CO
2-CH
4The poor N of-CO-
2-H
2System or gas reforming gas CO
2-CH
4-poor N
2-H
2System or take off CO
2Coal gas CO-CH
4-H
2Or take off CO
2Conversion gas CH
4-H
2The sepn process of system, unstripped gas is formed ammonia product or its conversion gas or the natural gas hydrogen preparation conversion gas that is similar to routine.Conversion gas pressure varying adsorption decarburization process in the ammonia synthesis process can be used for reference the variable pressure gas absorption that is applied in the technology of the present invention and take off CO
2Step; CH
4The poor N of-CO-
2-H
2System or CH
4-H
2The sepn process of system, unstripped gas is formed the natural gas hydrogen preparation device PSA hydrogen purification unstripped gas that is similar to routine, and natural gas hydrogen preparation device PSA hydrogen purification pressure swing adsorption technique can be used for reference the variable pressure gas absorption hydrogen purification step that is applied in the technology of the present invention.For these reasons, this partial content of description is exceeded in the present invention.This paper mainly describes relevant special content of the present invention.
CO in the raw gas internal recycle of the present invention path
2Separate part PSA1008 needs certain CO usually owing to go into producer gas
2Content so separate part PSA1008 bypass A is set usually, regulates producer gas CO
2Content.
CO in the raw gas internal recycle of the present invention path
2Separate part PSA1008 is owing to can contain CO from ring coal gas
2So, may need separate part PSA1008 bypass B, regulate from ring coal gas CO
2Content.
There is CO usually in the present invention
2Outer circulation, this is because the combustion processes and the CO conversion process of combustion chamber certainly lead to CO
2,, must carry out CO for its final discharger
2With separating of other component, owing to can not realize absolute the separation, and have a spot of CO of ratio in the coal gas usually
2Easier component that is adsorbed such as water, hydrogen sulfide, carbon three hydrocarbon, ethene are so in order to separate and to recycle these components, utilize CO usually
2Outer circulation is brought said components into the charring furnace combustion chamber.On this basis, look the particular case of concrete device, consider whether to be provided with CO
2Internal recycle, criterion is an economy certainly, main restricted factor is CO
2The internal recycle flow, CO
2The internal recycle flow is uneconomical very little the time, does not set up independently internal recycle coal gas CO this moment usually
2Separate part PSA1008.
Below detailed description is of the present invention takes off CO from ring coal gas
2Transformation absorbed portion 2008.
The present invention takes off CO from ring coal gas
2Transformation absorbed portion 2008 is according to CO
2Absorb leading-edge is constantly boosted in adsorption process, after absorption finishes, and CO
2Between forward position and outlet the one unsaturation adsorption zone and the principle of adsorption zone are not arranged, adsorption tower is divided into upper and lower two sections treats, hypomere is a high concentration CO
2Adsorption zone, epimere are lower concentration CO
2Adsorption zone and adsorption zone not.Take off CO
2The transformation absorbed portion behind adsorption process and the drop pressure end of processing, is provided with forward vacuum desorption step, emits high-purity CO from the middle discharge outlet of exit end or top
2Gas is controlled the pressure when forward the vacuum desorption step finishes as discharging gas, water, hydrogen sulfide, carbon three hydrocarbon, ethene is retained in the adsorption bed emits as the CO that returns the combustion chamber from inlet end in reverse vacuum desorption step then
2Outer circulation gas, its effect are the carbonic acid gas stripping gass of collecting rich hydrogen sulfide, carbon three hydrocarbon, ethene under the reasonable desorption condition of sorbent material, realize obtaining the purpose of three product separation.
The present invention takes off CO from ring coal gas
2Each adsorption tower of transformation absorbed portion experiences following steps successively in once circulating:
1. adsorb A: unstripped gas is sent into the adsorption bed opening for feed that is in adsorption step adsorb, sorbent material optionally adsorbs easy adsorbent component CO in the bed
2, H
2O etc., and in bed, set up easy adsorbent component adsorption zone, be difficult for component (as hydrogen, nitrogen, carbon monoxide, methane etc.) and a part of CO of absorption relatively
2Discharge by whole adsorption bed and from exit end, easily adsorbent component adsorption zone continuous exit end to bed in adsorption process moves, and when gas concentration lwevel reaches certain value in working off one's feeling vent one's spleen, ends unstripped gas, stops absorption.
2. equal pressure drop ED: after absorption finished, dead space gaseous hydrogen in the adsorption bed, nitrogen concentration were very high, and this part gas need be recycled, when this part gas is discharged from the bed outlet, and CO
2Concentration will increase gradually.Other bed of having finished evacuation step that this part gas can be used for this group boosts, and according to adsorptive pressure, bed number, the bed number average pressure drop pressure that is in adsorbed state simultaneously can be divided into repeatedly carries out.Each drop pressure gas carries out boost pressure to other different beds.The present invention, adsorption process pressure is between 0.15～1.5MPa (absolute pressure), select 0.20～0.6MPa (absolute pressure) usually.Adsorption process pressure needs when 0.15～0.7MPa (absolute pressure) all to press step 4 or 5 times usually, adsorption process pressure needs when 0.7～1.0MPa (absolute pressure) all to press step 6 times usually, and adsorption process pressure needs 7 times when 1.0～1.5MPa (absolute pressure) usually; During the drop pressure end of processing, adsorption column pressure is between 0.12～0.13MPa (absolute pressure);
3. vacuumizing and exhausting PP forward: from tower top or the middle part carbon dioxide enriched gas the tower is extracted out, promptly obtain carbon dioxide enriched gas; When this step finished, adsorption column pressure was between 0.04～0.06MPa (absolute pressure), usually can guarantee carbon dioxide enriched atmospheric carbon dioxide concentration to be not less than desired value combustibleconstituents concentration not to be higher than desired value be pressure low limit; This control causes CO
2The variation of internal circulating load;
4. the reverse VC that vacuumizes: from tower bottom entrap bubble in the tower is extracted out, promptly obtained being rich in the CO of components such as hydrogen sulfide, water, hydrogen sulfide, carbon three hydrocarbon, ethene
2Gas; When this step finished, adsorption column pressure was between 0.003～0.03MPa (absolute pressure), was pressure low limit can satisfy thoroughly the regenerate pressure condition of index of sorbent material usually;
5. boost pressure ER: utilize the adsorption bed expellant gas of drop pressure ED step, enter from exit end and finish the adsorption bed that vacuumizes step, make its pressure that progressively raises, all voltage rise can be carried out repeatedly.Each gas of accepting is from the equal pressure drop gas of different beds.
6. FR finally boosts: utilize adsorption step to work off one's feeling vent one's spleen and from the outlet side bed is boosted, be raised to adsorptive pressure.
The present invention takes off CO
2Transformation fractionation by adsorption part absorption working condition operational condition is: adsorbent bedly constitute the layering combination cot for a kind of in the activated alumina, gac, silica gel or by wherein several, the hydrogen sulfide volumetric concentration of purified gas usually less than 30PPm, be generally less than 20PPm, especially less than 10PPm, stripping gas carbonic acid gas volumetric concentration usually greater than 90%, generally greater than 92%, especially greater than 95%.
Below describe in detail of the present invention from ring coal gas hydrogen purification transformation absorbed portion 2009.
Purified hydrogen transformation absorbed portion adsorption tower of the present invention can arrange forward to put the pressure desorption procedure, and its effect is to collect rich nitrogen stripping gas under the reasonable desorption condition of sorbent material, realizes carrying from conversion gas dense N
2, for carrying dense CH
4Create conditions; Purified hydrogen transformation absorbed portion adsorption tower of the present invention, reverse vacuum desorption step is arranged, its effect is to collect the methane rich stripping gas as final desorption procedure (such as after forward putting pressure (collecting rich nitrogen gas) step), realizes carrying dense methane from conversion gas, can be used as high performance fuel gas.
The present invention experiences following steps successively from each adsorption tower of ring coal gas hydrogen purification transformation absorbed portion in once circulating:
1. adsorb A: will take off CO
2Purified gas is sent into the adsorption tower feed end that is in adsorption step in the adsorption tower and is adsorbed, and sorbent material is optionally adsorbed methane, N successively
2And in bed, set up the adsorption zone of easy adsorbent component, the components such as hydrogen that are difficult for absorption are discharged from the product end by adsorption bed, the impurity composition adsorption zone in adsorption process constantly the product end to bed move, when absorb leading-edge moves to the trough position of bed, stop absorption;
2. drop pressure ED: after absorption finishes, bed dead space gas needs further to reclaim, to several times gas be discharged in the bed from adsorption bed product end, this part gas can be used for two workshop sections other finished the bed that vacuumizes step and boosted, also can be used for boosting of workshop section's adsorption tower bed.Drop pressure can be carried out several times, and each drop pressure gas is all calmed the anger to other different beds and boosted; The present invention, adsorption process pressure is between 0.5～2.0MPa (absolute pressure), select 0.70～1.3MPa (absolute pressure) usually.The present invention, adsorption process pressure needs when 0.7～1.0MPa (absolute pressure) all to press step 4 times usually, and adsorption process pressure needs 5 times when 1.0～1.5MPa (absolute pressure) usually; During the drop pressure end of processing, adsorption column pressure is between 0.25～0.4MPa (absolute pressure);
3. exhaust PP forward: all press finish after, as the adsorptive pressure height, all press number of times more after a little while, all press and finish back bed internal pressure and be higher than normal atmosphere, need further bed step-down this moment, step-down can be carried out along the absorption direction, also can be against the operation of absorption direction.If raw gas contains a large amount of nitrogen, this part gas nitrogen is dense, and recyclable utilization is usually used as low calorie fuels gas or system nitrogen unstripped gas; The present invention, when forward exhaust process finished, adsorption column pressure was between 0.20～0.25MPa (absolute pressure);
4. reverse venting VC: to regenerate in order making in the bed, to utilize the bed overbottom pressure, adopt the reverse way of pressure of putting the portion C O of absorption
2, ethane, methane releases from the feed end of tower, makes bed obtain regeneration; As the case may be, behind step-down PP end of processing forward, adsorption column pressure is during near normal pressure, reverse venting step cancellation; Usually depend on the reverse methane concentration of calming the anger of putting; The present invention, during the inverted ventilating end of processing, adsorption column pressure is a pressure low limit with the pressure condition that can directly send into gas holder between 0.13～0.15MPa (absolute pressure) usually;
5. the reverse VC of vacuumizing:, adopt the reverse way that vacuumizes the CO of absorption in order to make thoroughly regeneration in the bed
2, ethane, methane releases from the feed end of tower, makes bed obtain regeneration.Usually the reverse stripping gas that vacuumizes enters gas holder after overdraft is boosted, and finally can be used as high performance fuel gas; The present invention, during the inverted ventilating end of processing, adsorption column pressure is between 0.02～0.05MPa (absolute pressure), is pressure low limit can satisfy thoroughly the regenerate pressure condition of index of sorbent material usually;
6. equal voltage rise ER: after finding time to finish, utilize the equal pressure drop gas of other bed to enter this adsorption tower, it is boosted from the product end.Equally, all voltage rise can repeatedly be carried out, and the gas that at every turn is used for equal voltage rise is from the different beds equal pressure drop gas of same order workshop section not.
7. FR finally boosts: after all rising end, bed layer pressure does not also reach the requirement of adsorptive pressure, and a part of product gas that discharge with a part of adsorption bed that is in adsorption step this moment boosts until adsorptive pressure to this adsorption bed.
Hydrogen purification transformation fractionation by adsorption part absorption working condition operational condition of the present invention is: adsorbent bedly constitute the layering combination cot for a kind of in the activated alumina, gac, silica gel, zeolite molecular sieve or by wherein several, hydrogen recovery rate usually greater than 85%, generally greater than 90%, especially greater than 95%, hydrogen product concentration usually greater than 95%, generally greater than 99%, especially greater than 99.9%.
Below describe transformation fractionation by adsorption part 3100 of the present invention and transformation fractionation by adsorption part 3200 in detail.
Efflux rich CO in order to reduce
2The H that stripping gas carries
2S and inflammable gas quantity need raising to efflux rich CO
2During stripping gas purity, can increase by one and be used for CO
2Put forward dense transformation fractionation by adsorption part 3100, (be rich in the CO of components such as hydrogen sulfide, water, hydrogen sulfide, carbon three hydrocarbon, ethene at the stripping gas of this acquisition
2Gas), return combustion chamber of the present invention usually.
The oxygen-enriched combusting charring process is in order to improve rich N
2Discharging gas purity can increase by one for this reason and be used for N
2The transformation fractionation by adsorption part 3200 of purifying, economic as far as possible simultaneously reduction effluxes rich N
2The inflammable gas quantity that gas carries needs control to efflux rich N
2Gas purity is at the stripping gas (being rich in components such as methane) of this acquisition, usually as fuel gas.
Below in conjunction with raw gas is that example is described the process of producing crude phenols in middle coalite tar of the present invention in detail, can use carbon dioxide enriched gas and rich nitrogen gas to be in harmonious proportion and prepare phenol sodium decomposition system crude phenols carbon dioxide air source.
As everyone knows, phenols is one of main Chemicals that exist in the coal tar, the composition of phenols is relevant with the condition of coal blending composition, coal blending character and coking operation with productive rate in the coal tar, phenols content fluctuation is bigger in the coal tar, and wherein major part is lower boiling phenols (phenol, cresols, an xylenol).The coking temperature is high more, and the phenols productive rate is low more, and wherein lower boiling phenol reduces, and higher phenols increases.
Table 7 pyrolysis of coal temperature and coal tar kind relation
| Sequence number | The pyrolysis of coal temperature, ℃ | The coal tar kind |
| 1 | 300～550 | Coalite tar |
| 2 | 550～750 | Coal-tar middle oil |
| 3 | 750～1000 | Middle coal-tar heavy oil |
| 4 | More than 1000 | Coal-tar heavy oil |
Phenol content is generally 1.0%～2.5% in the coal-tar heavy oil; The blue charcoal byproduct of coal system coal-tar middle oil phenol content is generally 3.0%～10.0%, and oil (oil waterborne) phenol content is generally 5.0%～30.0% in the coal gasification course byproduct coalite tar.That is to say the lower boiling phenols of middle coalite tar (phenol, cresols, xylenol) content height.
In middle coalite tar, extract phenol and have economic implications, this be because: on the one hand, because refining single phenol market height of lower boiling phenols (existing market price 1.2～1.5 ten thousand yuan/ton), along with the progressively increase of middle coalite tar process scale, the quantity of therefrom extracting lower boiling phenol in the coalite tar also progressively increases and possesses economy; On the other hand, therefrom extract phenol in the coalite tar,, therefore following advantage is arranged: 1. reduced the raw material acid number, alleviated the corrosion of equipment and equipment owing to reduced the oxygen level of coal tar hydrogenating unit hydrogenating materials; 2. reduce the output of hydrogenator stock oil heat-processed condenses, be beneficial to prolong operating period, improved the efficient of equipment such as interchanger, process furnace; 3. reduced the hydrogen consumption; 4. reduced water generation reaction quantity, reduced steam partial pressure, can reduce hydrogen/stock oil volume ratio, reduced the recycle hydrogen consumption, reduced the hydrogen gas circulating system scale, reduced construction investment, cut down the consumption of energy.
Application number with reference to the inventor is a kind of middle coalite tar working method of 201010592541.X, and the process of producing crude phenols in middle coalite tar generally includes following steps: at coal tar distillation part SEC1, fractionation feed coal tar obtains carbolic oil NPO; At carbolic oil alkali cleaning part SEC2, carbolic oil NPO finishes washing with alkali lye SHW by counter current contact and separates, and obtains final stage oil-containing phenol sodium water solution OPW and final stage dephenolize oil CDPO; At phenol sodium water solution de-oiling part SEC4, obtain de-oiling phenol sodium water solution; Decompose system crude phenols part SEC5 at phenol sodium, de-oiling phenol sodium water solution contacts with acidic substance and carries out the decomposition reaction of phenol sodium, obtains crude phenols.
Decompose system crude phenols part at described phenol sodium, de-oiling phenol sodium water solution contacts with acidic substance to be finished the decomposition reaction of phenol sodium and obtains crude phenols, using maximum process programs at present is sulfuric acid decomposition technique and carbonic acid gas decomposition technique, and these technologies can be learnt from the listed publication of table 8.
The publication of stripping oil technology and the clean de-oiling technology of light oil is steamed in table 8 record
When phenol sodium decomposes system crude phenols use sulfuric acid decomposition technique, obtain the 1kg crude phenols and need consume 100%H
2SO
4Quantity be roughly 0.6kg, the shortcoming of this method is: consume that sulfuric acid increases cost, produces sodium sulfate waste liquor contamination water body, the sodium sulfate waste liquid contains phenol and forms the phenol loss.
Carbonic acid gas decomposes phenol sodium technology and comprises the alkali lye working cycle, uses calcium oxide as the displacement alkali source, and the reaction of formation calcium hydroxide and V Soda generates CaCO in the aqueous solution
3With NaOH solution, remove CaCO through separation
3The recyclable NaOH solution of slag is used further to the dephenolize process, thereby forms the closed cycle of sodium hydroxide, and the NaOH rate of recovery can reach about 70～75%.Therefore, comparing the sulfuric acid decomposition technique, when having ready conditions, select the carbonic acid gas decomposition technique can reduce alkaline consumption significantly, reduce the phenolic wastewater quantity discharged, can improve the phenol products rate of recovery simultaneously, is preferred version.
Second stripping gas that technology of the present invention produces, decompose preparation crude phenols process carbon dioxide air source through handling (pressurization, attemperation) back as phenol sodium, in the occasion of not having other more suitable carbon dioxide air source, enlarged phenol sodium carbonic acid gas and decomposed legal system crude phenols Application Areas.
The present invention is treated to phenol sodium with second stripping gas and decomposes preparation crude phenols process and need attemperation usually with the process of carbon dioxide air source, be about to 35～45 ℃ and adjust to 55～65 ℃, can adopt any effective means, such as with the hot flue gas heat exchange of process furnace, or with the suitable direct mixing preparation of heating furnace high-temperature flue gas, or feed the water vapor etc. of heat.
The present invention is treated to phenol sodium with second stripping gas and decomposes preparation crude phenols process and may need to regulate gas concentration lwevel with the process of carbon dioxide air source, be about to adjust to 15～20% scopes, can adopt any effective means, such as be in harmonious proportion with other flue gas of heating furnace, or be in harmonious proportion etc. with secondary emission gas PG2F.
Known phenol sodium carbonic acid gas decomposes the legal system crude phenols and is once by flow process and decomposes mass transfer workshop section with carbon dioxide air source and be divided into two workshop sections and use the fresh carbon dioxide source of the gas separately, still reactionless back gas is as the report of carbon dioxide air source recycle scheme, yet for higher the present invention's second stripping gas of concentration, the conventional application that has once limited the carbonic acid gas decomposition method by flow process.The present invention utilizes the high characteristics of the second stripping gas gas concentration lwevel, proposes recycle part secondary emission gas PG2F and necessitates and practical technique in some occasions, and its advantage is:
1. under the constant prerequisite of phenol sodium raw materials quantity, decompose mass transfer workshop section and can significantly reduce, can reduce the scale of smoke pre-heating system significantly with fresh carbon dioxide source of the gas quantity;
2. the carbonic acid gas volumetric concentration of the carbon dioxide air source that contacts with phenol sodium water solution (water-content about 60%, phenol sodium about 40%) in guaranteeing mass transfer workshop section (decomposing part mass transfer workshop section and acidifying part mass transfer workshop section) is not less than under the prerequisite of Schwellenwert (such as 13%), under the constant prerequisite of fresh smoke amount, phenol sodium raw materials processing quantity can increase considerably.
Second stripping gas decomposes preparation crude phenols process by phenol sodium and is converted into secondary emission gas PG2F, owing to consumed carbonic acid gas, improved secondary emission gas PG2F butt volume calorific value simultaneously, suppose the second stripping gas carbonic acid gas volume content 30%, secondary emission gas PG2F carbonic acid gas volume content 10%, it is about 28% that butt volume calorific value can improve, and secondary emission gas PG2F is more suitable in as low-sulfur fuel gas or fuel gas blending stock.Secondary emission gas PG2F may need cooling to divide water as before the low-sulfur fuel gas.
Certainly, when condition was suitable, second stripping gas gas that also can act as a fuel earlier used, uses then the fuel gas flue gas to decompose legal system crude phenols carbon dioxide air source as phenol sodium carbonic acid gas.
Below describe rich CO of the present invention in detail
2Gas is used as phenol sodium carbonic acid gas and decomposes the concrete using method of legal system crude phenols with carbon dioxide air source.
Decompose system crude phenols part at described phenol sodium, de-oiling phenol sodium water solution contacts with carbon dioxide air source to be finished the decomposition reaction of phenol sodium and obtains crude phenols, comprising decomposing workshop section and acidifying workshop section, carbon dioxide air source is divided into three tunnel first via carbon dioxide air source, the second road carbon dioxide air source and the Third Road carbon dioxide air sources that use in parallel usually.Decompose mass transfer workshop section first, first via carbon dioxide gas is derived from the bottom and enters the first decomposition mass transfer workshop section, phenol sodium enters first and decomposes mass transfer workshop section from the top, phenol sodium flows from top to bottom and the carbon dioxide containing gas counter current contact that rises is carried out the decomposition reaction of phenol sodium carbonic acid gas, first decomposes mass transfer workshop section top gas discharges the first decomposition mass transfer workshop section from the top, first decomposes mass transfer workshop section bottom liquid decomposes mass transfer workshop section from bottom discharge first; Decompose mass transfer workshop section second, the second road carbon dioxide gas is derived from the bottom and enters the second decomposition mass transfer workshop section, first decomposes mass transfer workshop section bottom liquid enters the second decomposition mass transfer workshop section from the top, first decomposes the mobile carbon dioxide containing gas counter current contact with rising of mass transfer workshop section bottom liquid from top to bottom carries out the decomposition reaction of phenol sodium carbonic acid gas, second decomposes mass transfer workshop section top gas discharges the second decomposition mass transfer workshop section from cat head, and second decomposes mass transfer workshop section bottom liquid decomposes mass transfer workshop section from bottom discharge second; Decompose mass transfer workshop section bottom liquid separate part second, second decomposes mass transfer workshop section bottom liquid is separated into crude phenols primary product and aqueous sodium carbonate; Contain the high boiling point phenates in the crude phenols primary product; In acidifying mass transfer workshop section, the Third Road carbon dioxide gas is derived from lower curtate and enters acidifying mass transfer workshop section, the crude phenols primary product enters acidifying mass transfer workshop section from the top, the crude phenols primary product flows from top to bottom and the carbon dioxide containing gas counter current contact that rises is carried out the decomposition reaction of phenates carbonic acid gas, acidifying mass transfer workshop section top gas is discharged acidifying mass transfer workshop section from the top, acidifying mass transfer workshop section bottom liquid is discharged acidifying mass transfer workshop section from the bottom; At acidifying mass transfer workshop section bottom liquid separate part, acidifying mass transfer workshop section bottom liquid is separated into crude phenols and aqueous sodium carbonate.
Decompose system crude phenols part at described phenol sodium, de-oiling phenol sodium water solution contacts with carbon dioxide air source to be finished the decomposition reaction of phenol sodium and obtains crude phenols, comprising decomposing workshop section and acidifying workshop section, its operational condition is generally as follows: in the described carbon dioxide air source carbonic acid gas volumetric concentration generally greater than 10%, usually greater than 15%, be preferably 15～20%; Decompose mass transfer workshop section first, mass transfer workshop section number of theoretical plate is generally 2～30, is generally 10～20, working pressure is generally 0.12～0.18MPa (absolute pressure), is generally 0.12～0.14MPa (absolute pressure), the phenol sodium temperature that enters mass transfer workshop section is generally 60～70 ℃, is generally 55～65 ℃, the carbon dioxide containing gas feeding temperature is 35～70 ℃, and mass transfer workshop section temperature of reaction is 50～70 ℃; Decompose mass transfer workshop section second, mass transfer workshop section number of theoretical plate is generally 2～30, is generally 10～20, working pressure is generally 0.12～0.18MPa (absolute pressure), is generally 0.12～0.14MPa (absolute pressure), the first decomposition mass transfer workshop section bottom liquid temperature that enters mass transfer workshop section is 60～70 ℃, the carbon dioxide containing gas feeding temperature is 35～70 ℃, and mass transfer workshop section temperature of reaction is generally 50～60 ℃, is generally 53～57 ℃; Decompose the mass transfer bottom liquid separate part SP1 of workshop section second, the weight content that obtains is the aqueous sodium carbonate of 10～15% (weight); Contain the high boiling point phenates in the crude phenols primary product that obtains; In acidifying mass transfer workshop section, mass transfer workshop section number of theoretical plate is generally 2～30, is generally 8～25, working pressure is generally 0.12～0.18MPa (absolute pressure), is generally 0.12～0.14MPa (absolute pressure), the crude phenols primary product temperature that enters mass transfer workshop section is 50～70 ℃, the carbon dioxide gas source temperature is 35～70 ℃, 2～30 of mass transfer workshop section number of theoretical plates, mass transfer workshop section temperature of reaction are generally 50～60 ℃, are generally 53～57 ℃.The Action Target that described phenol sodium decomposes system crude phenols part is: decompose the overall rate of decomposition of part sodium phenolate generally greater than 98%, usually greater than 99%; In acidifying mass transfer workshop section, the sodium phenolate rate of decomposition generally greater than 99%, usually greater than 99.5%.Each step of decomposing system crude phenols part at described phenol sodium, total carbon dioxide capacity control is as follows in the gas feed: decompose mass transfer workshop section first, the ratio of the theoretical consumption of total carbon dioxide capacity and phenol sodium decomposition and consumption carbonic acid gas is generally 2～5, is generally 2～3 in the gas feed; Decompose mass transfer workshop section second, the ratio of the theoretical consumption of total carbon dioxide capacity and phenol sodium decomposition and consumption carbonic acid gas is generally 8～14, is generally 9～12 in the gas feed.Crude phenols according to described carbonic acid gas decomposition technique obtains can satisfy table 9 quality index.
Table 9 crude phenols quality index
| Project | Desired value |
| The massfraction of phenol and homologue thereof (moisture-free basis), % | ≥83 |
| Cut (moisture-free basis) | ? |
| Quantity of distillate before 210 ℃ (volume fraction), % | ≥60 |
| Quantity of distillate before 230 ℃ (volume fraction), % | ≥85 |
| Neutral oil content, % | ≤0.8 |
| Pyridine base content, % | ≤0.5 |
| pH | 5～6 |
| Ignition residue content, % | ≤0.4 |
| Moisture, % | ≤10 |
Charring furnace of the present invention combustion chamber uses oxygen rich gas to replace air usually, and the present invention does not carry out any qualification to the oxygen enrichment technology of preparing, and a kind of air method for oxygen enriching is seen the description of embodiment four.
Fuel element of the present invention can be raw gas and or high methane gas, also can be that the outer external gas of device is as containing the suitable gas of ethane, propane, CO.
Below describe the method that the present invention prepares methanol feedstock gas in detail.
The present invention possesses following characteristics from ring coal gas, is suitable for as methanol feedstock gas:
1. H
2With CO concentration sum height, and H
2/ CO molecular ratio belongs to rich carbon gas usually less than 2;
2. H
2/ CO molecular ratio is easy to regulate, and adopts conversion process to get final product;
3. ethane and heavy hydrocarbons content thereof are low and be easy to further remove, and adopt PSA technology to get final product;
4. methane content is low, can not remove;
5. because methane vapor transforms system H
2Be one with the process of CO and generate gas H
2Superfluous process so adopt methane vapor to transform when improving raw material availability, can also obtain and regulate H
2The effect of/CO molecular ratio can improve H simultaneously
2, CO, CH
4Comprehensive utilization ratio;
6. utilize CO conversion process reaction heat to form high temperature shift gas, high temperature shift gas directly enters the methane vapor conversion process, further, because the reforming gas vapour content is lower, reforming gas directly enters methanol synthesizer methanol sythesis reactor (or with the lower circulation gas of temperature mixes then enter methanol sythesis reactor) with suitable high state of temperature, thus the formation integrated technique.
Below describe characteristic of the present invention in detail.
A kind of with CO
2Coal carbonization technology for combustion processes temperature control component is characterized in that comprising following steps:
1. gas making partly comprises charring furnace and coking chamber heat-carrying component internal circulation system, and charring furnace comprises the combustion chamber of fuel gas and the coking chamber of coal;
In coking chamber, according to the advance route of coal charge, being divided into first section is that coal preheating section (or claim gas cooling section), second section are that coal carbonization section, the 3rd section are charcoal cooling section (or claiming gas preheating section); In the 3rd section zone, comprise the first via gas of coking chamber heat-carrying component and two sections process material contact heat-exchangings and reclaim and become three sections process gas after its heat heats up, three sections process material leave three sections zones; In second section zone, gas fume of combustion chamber, three sections process gas carry out gas-solid with one section process material and directly contact generation charing effect, and two sections process material leave second section zone and enter the 3rd section zone, and two sections process gas leave second section zone and enter first section zone; In first section zone, after transmitting the heat cooling and sneak into one section generation gas with the outside certainly coal charge Contact Heating coal charge that adds, two sections process gas become one section product gas (raw gas), and become one section process material after coal charge heats up and enter second section zone;
At least a portion is returned coking chamber as coking chamber heat-carrying component based on the logistics of raw gas, constitutes gas making part coking chamber heat-carrying component internal recycle;
Gas making part coal gas product is as leaving the gas making part from ring coal gas;
It is characterized in that: the combustion chamber oxygen donator is oxygen enrichment or pure oxygen, with CO
2Be main combustion chamber temperature control component;
The definition of combustion chamber temperature control component is: from the charring furnace outside, the coexistence of combustion chamber and fuel element, possess the control combustion product gases temperature function, that do not participate in combustion reactions, pass the combustion chamber and pass that coking chamber contacts with coal charge, enter the non-combustibleconstituents in the raw gas when leaving charring furnace.
Combustion chamber CO
2The temperature control component ratio of component usually greater than 0.50, generally greater than 0.85 more preferably greater than 0.95.The definition of combustion chamber temperature control component ratio is: the ratio of specific combustion chamber temperature control component volume and whole combustion chambers temperature control component volume.5, method according to claim 2 is characterized in that:
Combustion chamber CO
2The temperature control component ratio of component, make the combustion chambers burn flue-gas temperature finally satisfy coking chamber charing section temperature index: lump coal is heated to by this section and is generally 600～850 ℃, is generally 750～850 ℃, is preferably 780～820 ℃ temperature.
Combustion chamber CO
2The temperature control component ratio of component, to make the combustion chambers burn flue-gas temperature be generally 600～900 ℃, be generally be 700～900 ℃, be preferably 750～850 ℃.
The whole feeding gas in combustion chamber of the present invention satisfy following regulation usually: the whole feeding gas in combustion chamber are divided into virtual oxygen donator and virtual fuel body; Virtual oxygen donator is by oxygen components and the CO of first part
2Component constitutes, the CO of first part
2The ratio of component volume amount and oxygen components volume amount calculates (being that the oxygen components volumetric concentration is 16～40% in the virtual oxygen donator), CO by 1.50～5.25
2The temperature control component ratio of component is greater than 0.50; Virtual fuel body volume calorific value is 1400～2600KCAL/Nm
3
The whole feeding gas in combustion chamber of the present invention satisfy following general provision: virtual oxygen donator is by oxygen components and the CO of first part
2Component constitutes, the CO of first part
2The ratio of component volume amount and oxygen components volume amount calculates (being that the oxygen components volumetric concentration is 21～35% in the virtual oxygen donator), CO by 1.85～3.76
2The temperature control component ratio of component is greater than 0.90; Virtual fuel body volume calorific value is 1700～2400KCAL/Nm
3
The present invention produces low CO
2During coal gas, it is characterized in that: 1. in the gas making part, raw gas enters transformation fractionation by adsorption part PSA1008 after at least a portion de-oiling from ring, and during absorption working condition, raw gas passes when adsorbent bed after the de-oiling, sorbent material selective adsorption CO
2And the easier component that is adsorbed, H
2, CH
4, component such as CO passes adsorbent bed becoming and takes off CO
2Coal gas; At least a portion is taken off CO
2Coal gas returns the charring furnace coking chamber as coking chamber heat-carrying component, forms coking chamber heat-carrying component internal recycle gas; During the desorb operating mode, obtain rich CO
2Gas, the rich CO of at least a portion
2Gas returns the charring furnace combustion chamber combustion chamber temperature control component is provided, and forms combustion chamber temperature control component internal recycle gas; Do not return the coal gas (raw gas and or take off CO of charring furnace in gas making part
2Coal gas) be used as from ring coal gas.
The present invention in the gas making part, isolates rich CO based on the logistics employing variable-pressure adsorption separating method of de-oiling raw gas
2Gas, the rich CO of at least a portion
2Gas returns the charring furnace combustion chamber combustion chamber temperature control component is provided, and forms combustion chamber temperature control component internal recycle gas.
The present invention in the gas making part, adopts variable-pressure adsorption separating method to isolate based on the logistics of de-oiling raw gas and takes off CO
2Coal gas, at least a portion is taken off CO
2Coal gas returns the charring furnace coking chamber coking chamber heat-carrying component is provided, and forms coking chamber heat-carrying component internal recycle gas.
The present invention from ring coal gas processing part, adopts variable-pressure adsorption separating method to isolate rich CO based on the logistics from ring coal gas
2Gas WH, at least a portion WH return the charring furnace combustion chamber and make combustion chamber temperature control component, form combustion chamber temperature control component outer circulation gas.
The present invention from ring coal gas processing part, adopts variable-pressure adsorption separating method to isolate poor H based on the logistics from ring coal gas
2, poor CO
2Gas returns the charring furnace combustion chamber combustion chamber fuel element is provided, and forms combustion chamber fuel element outer circulation gas.
The present invention forms when producing high performance fuel gas technology, and it is characterized in that: 1. in the gas making part, raw gas enters transformation fractionation by adsorption part PSA1008 after the de-oiling, during absorption working condition, after the de-oiling raw gas pass adsorbent bed, sorbent material selective adsorption CO
2And the easier component that is adsorbed, H
2, CH
4, component such as CO passes the adsorbent bed high heating value gas that becomes, a part of high heating value gas returns the charring furnace coking chamber, as coking chamber heat-carrying component, forms coking chamber heat-carrying component internal recycle gas.The operational condition of transformation fractionation by adsorption separate part PSA1008 is generally: adsorption process pressure is between 0.13～0.5MPa (absolute pressure); During the drop pressure end of processing, adsorption column pressure is between 0.07～0.13MPa (absolute pressure); The reverse step that vacuumizes is when finishing, and adsorption column pressure is between 0.003～0.03MPa (absolute pressure); Adsorbent bedly constitute layering combination cot, the CO of purified gas for a kind of in the activated alumina, gac, silica gel or by wherein several
2Volumetric concentration is less than 15%, and stripping gas carbonic acid gas volumetric concentration is greater than 90%.The operational condition preferably of transformation fractionation by adsorption separate part PSA1008 is: adsorption process pressure is between 0.15～0.3MPa (absolute pressure); Adsorbent bed is the layering combination cot that activated alumina, silica gel constitute, the CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%.Transformation fractionation by adsorption part PSA1008, partly or entirely stripping gas returns the charring furnace combustion chamber, and combustion chamber temperature control component is provided, and forms combustion chamber temperature control component internal recycle gas.
The present invention forms first kind when ring gas production hydrogen and fuel gas technology, it is characterized in that: 2. comprise hydrogen purification part PSA2089 from ring coal gas processing part; In the PSA2089 part, during absorption working condition, unstripped gas passes when adsorbent bed, and sorbent material selective adsorption non-hydrogen components, hydrogen component are passed the adsorbent bed PSA2089 of becoming purified gas, and the PSA2089 stripping gas is as fuel gas.The operational condition of PSA2089 is generally: adsorption process pressure is between 0.5～2.5MPa (absolute pressure); During the drop pressure end of processing, adsorption column pressure is between 0.25～0.40MPa (absolute pressure); When reverse deflation course finished, adsorption column pressure was between 0.13～0.15MPa (absolute pressure); Adsorbent bedly constitute layering combination cot, the H of purified gas for a kind of in the gac, silica gel, zeolite molecular sieve or by wherein several
2Volumetric concentration is greater than 95%, H
2The volume yield is greater than 92%.The operational condition of PSA2089 is generally: adsorption process pressure is between 0.6～1.5MPa (absolute pressure); The reverse VC step that vacuumizes is when finishing, and adsorption column pressure is between 0.02～0.05MPa (absolute pressure); The H of purified gas
2Volumetric concentration is greater than 99%, H
2The volume yield is greater than 90%.
The present invention forms second kind when ring gas production hydrogen and fuel gas technology, it is characterized in that: 2. comprise from ring coal gas processing part and take off CO
2Part PSA2008 and hydrogen purification part PSA2009; In the PSA2008 part, during absorption working condition, unstripped gas passes when adsorbent bed, sorbent material selective adsorption CO
2And the easier component that is adsorbed, H
2, CH
4, component such as CO passes the adsorbent bed PSA2008 of becoming purified gas, at least a portion PSA2008 stripping gas returns the charring furnace combustion chamber, and combustion chamber temperature control component is provided, and forms combustion chamber temperature control component outer circulation gas; In the PSA2009 part, during absorption working condition, unstripped gas passes when adsorbent bed, and sorbent material selective adsorption non-hydrogen components, hydrogen component are passed the adsorbent bed PSA2009 of becoming purified gas, and the PSA2009 stripping gas is as high methane gas.Take off CO
2The operational condition of part PSA2008 is generally: adsorption process pressure is between 0.2～0.8MPa (absolute pressure); During the drop pressure end of processing, adsorption column pressure is between 0.07～0.13MPa (absolute pressure); The reverse VC step that vacuumizes is when finishing, and adsorption column pressure is between 0.003～0.03MPa (absolute pressure); Adsorbent bedly constitute layering combination cot, the CO of purified gas for a kind of in the activated alumina, gac, silica gel or by wherein several
2Volumetric concentration is less than 15%, and stripping gas carbonic acid gas volumetric concentration is greater than 90%.The operational condition of hydrogen purification part PSA2009 is generally: adsorption process pressure is between 0.5～2.5MPa (absolute pressure); During the drop pressure end of processing, adsorption column pressure is between 0.25～0.40MPa (absolute pressure); When reverse deflation course finished, adsorption column pressure was between 0.13～0.15MPa (absolute pressure); Adsorbent bedly constitute layering combination cot, the H of purified gas for a kind of in the gac, silica gel, zeolite molecular sieve or by wherein several
2Volumetric concentration is greater than 95%, H
2The volume yield is greater than 90%.
The present invention forms the third when ring gas production hydrogen and fuel gas technology, it is characterized in that: 2. comprise carbon monodixe conversion part 2100 from ring coal gas processing part and take off CO
2Part PSA2008 and hydrogen purification part PSA2009; Carbon monodixe conversion hydrogen manufacturing part 2100 operational conditions are generally: the carbon monoxide transformation efficiency greater than 85%, oxygen all transforms, the organosulfur transformation efficiency is greater than 85%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.8MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that the molecular ratio of 300～2500 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide is 1.3～6.0 that average reaction temperature is lower than 350 ℃, pressure; Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA2008; Take off CO
2The operational condition of part PSA2008 is generally: adsorption process pressure is between 0.2～0.7MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%.The operational condition of hydrogen purification part PSA2009 is generally: adsorption process pressure is between 0.6～1.5MPa (absolute pressure); The reverse VC step that vacuumizes is when finishing, and adsorption column pressure is between 0.02～0.05MPa (absolute pressure); The H of purified gas
2Volumetric concentration is greater than 99%, H
2The volume yield is greater than 94%.Carbon monodixe conversion hydrogen manufacturing part 2100 operational conditions are generally: the carbon monoxide transformation efficiency greater than 90%, oxygen all transforms, the organosulfur transformation efficiency is greater than 90%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.6MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that 500～2000 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide molecule ratio are 1.5～4.5 that average reaction temperature is lower than 300 ℃, pressure; Enter after conversion gas reduction temperature to the 35～45 ℃ dehydration and take off CO
2Part PSA2008; Take off CO
2The operational condition of part PSA2008 is generally: adsorption process pressure is between 0.2～0.5MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%.The operational condition of hydrogen purification part PSA2009 is generally: adsorption process pressure is between 0.7～1.2MPa (absolute pressure); The H of purified gas
2Volumetric concentration is greater than 99%, H
2The volume yield is greater than 96%.Carbon monodixe conversion hydrogen manufacturing part 2100 operational condition preferablies are: the carbon monoxide transformation efficiency greater than 95%, oxygen all transforms, the organosulfur transformation efficiency is greater than 95%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.5MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that 800～1500 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide molecule ratio are 1.5～3.5 that average reaction temperature is lower than 250 ℃, pressure; Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA2008; The operational condition of transformation fractionation by adsorption separate part PSA2008 preferable be: adsorption process pressure is between 0.15～0.4MPa (absolute pressure); Adsorbent bed is that activated alumina, silica gel constitute layering combination cot, the CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%.
The present invention forms when ring coal gas main product hydrogen technology, and it is characterized in that: 2. at hydrogen purification part PSA2009, partly or entirely the PSA2009 stripping gas returns the charring furnace combustion chamber, and the combustion chamber fuel element is provided, and forms combustion chamber fuel element outer circulation gas.
The invention provides combustion chamber temperature control component CO
2Logistics can be used as the heat-obtaining body, provide combustion chamber temperature control component CO such as at least a portion
2Logistics and the high-temperature flue gas heat exchange of boiler after the hot gas of gained enter the combustion chamber, perhaps provide combustion chamber temperature control component CO such as at least a portion
2Logistics and the heat exchange of sulfur recovery facility high-temperature tail gas after the hot gas of gained enter the combustion chamber.
The invention provides combustion chamber temperature control component CO
2Logistics can be technology with pressure discharging gas, provide combustion chamber temperature control component CO such as at least a portion
2Logistics be discharging gas from coal preparing natural gas process.
The present invention forms when ring coal gas system methanol feedstock gas technology, it is characterized in that: 1. from ring coal gas processing part, at least a portion from ring coal gas as making methanol feedstock gas.
The present invention forms first kind when ring coal gas system methanol feedstock gas technology, and common operational condition is: 2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.0～2.5.Comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.5～2.0; Carbon monodixe conversion hydrogen manufacturing part 3100 operational conditions are: the carbon monoxide transformation efficiency is regulated conversion gas H
2/ CO molecular ratio is 1.5～2.5, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that the molecular ratio of 3.0～15MPa (absolute pressure), water vapor/carbon monoxide is 0.7～2.5 that average reaction temperature is lower than 350 ℃, pressure; The hot conversion gas that leaves shift-converter enters methanol sythesis reactor.
The present invention forms first kind when ring coal gas system methanol feedstock gas technology, and general operational condition is: 2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.5～2.0; Carbon monodixe conversion hydrogen manufacturing part 3100 operational conditions are: the carbon monoxide transformation efficiency is regulated conversion gas H
2/ CO molecular ratio is 1.5～2.5, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that the molecular ratio of 3.0～15MPa (absolute pressure), water vapor/carbon monoxide is 0.7～2.5 that average reaction temperature is lower than 350 ℃, pressure; The hot conversion gas that leaves shift-converter enters in the circulation gas raw material of methanol sythesis reactor.
The present invention forms first kind when ring coal gas system methanol feedstock gas technology, and preferable operational condition is: 2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.5～2.0; Take off the impurity step from ring coal gas through hydrogenation, organosulfur is converted into hydrogen sulfide, oxygen is converted into water, reforming gas is divided into two-way, and first via reforming gas obtains conversion gas, the H of the gas mixture of the conversion gas and the second road reforming gas through carbon monodixe conversion part 3100
2/ CO molecular ratio is 1.5～2.0.
The present invention forms first kind when ring coal gas system methanol feedstock gas technology, the operational condition of carbon monodixe conversion part 3100 normally: 2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is adjusting conversion gas H
2/ CO molecular ratio is 1.5～2.0; Carbon monodixe conversion hydrogen manufacturing part 3100 operational conditions are: the carbon monoxide transformation efficiency greater than 50%, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that the molecular ratio of 3.0～15MPa (absolute pressure), water vapor/carbon monoxide is 0.7～2.5 that average reaction temperature is lower than 350 ℃, pressure.
The present invention forms first kind when ring coal gas system methanol feedstock gas technology, the operational condition of carbon monodixe conversion part 3100 generally is: 2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, carbon monodixe conversion hydrogen manufacturing part 2100 operational conditions are: the carbon monoxide transformation efficiency is greater than 65%.
The present invention forms first kind when ring coal gas system methanol feedstock gas technology, the operational condition preferably of carbon monodixe conversion part 3100 is: 2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, carbon monodixe conversion hydrogen manufacturing part 2100 operational conditions are: the carbon monoxide transformation efficiency is greater than 85%.
The present invention forms second kind when ring coal gas system methanol feedstock gas technology, operational condition normally: 2. comprise carbon monodixe conversion part 4100 from ring coal gas processing part, its function is adjusting conversion gas H
2/ CO molecular ratio is 1.5～2.0; Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA4108, PSA4108 takes off CO
2Gas is as system methanol feedstock gas;
The present invention forms second kind when ring coal gas system methanol feedstock gas technology, and operational condition generally is: 2. comprise carbon monodixe conversion part 4100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.5～2.0; Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA4108, PSA4108 takes off CO
2Gas is as system methanol feedstock gas; Carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: the carbon monoxide transformation efficiency is regulated conversion gas H
2/ CO molecular ratio is 1.5～2.0, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.8MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that the molecular ratio of 300～2500 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide is 0.7～2.0 that average reaction temperature is lower than 350 ℃, pressure; Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.2～0.7MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%.
The present invention forms second kind when ring coal gas system methanol feedstock gas technology, operational condition preferable be: 2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: carbon monoxide transformation catalyst bed working pressure is 0.3～0.6MPa (absolute pressure); Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.2～0.5MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%.
The present invention forms second kind when ring coal gas system methanol feedstock gas technology, and operational condition is preferably: 2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: carbon monoxide transformation catalyst bed working pressure is 0.3～0.5MPa (absolute pressure); Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.15～0.4MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%; Adsorbent bed is that activated alumina, silica gel constitute the layering combination cot.
The present invention forms the third when ring coal gas system methanol feedstock gas technology, operational condition is generally: 2. comprise carbon monodixe conversion part 4100 from ring coal gas processing part, take off the impurity step from ring coal gas through hydrogenation, organosulfur is converted into hydrogen sulfide, oxygen is converted into water, reforming gas is divided into two-way, first via reforming gas obtains conversion gas, the H of the gas mixture of the conversion gas and the second road reforming gas through carbon monodixe conversion part 4100
2/ CO molecular ratio is 1.5～2.0; Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA4108, PSA4108 takes off CO
2Gas is as system methanol feedstock gas;
The present invention forms the third when ring coal gas system methanol feedstock gas technology, and operational condition is generally: 2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: the carbon monoxide transformation efficiency is regulated conversion gas H
2/ CO molecular ratio is 1.5～2.0, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.8MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that the molecular ratio of 300～2500 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide is 0.7～2.0 that average reaction temperature is lower than 350 ℃, pressure; Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.2～0.7MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%.
The present invention forms the third when ring coal gas system methanol feedstock gas technology, operational condition preferable be: 2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: carbon monoxide transformation catalyst bed working pressure is 0.3～0.6MPa (absolute pressure); Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.2～0.5MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%.
The present invention forms the third when ring coal gas system methanol feedstock gas technology, and operational condition is preferably: 2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: carbon monoxide transformation catalyst bed working pressure is 0.3～0.5MPa (absolute pressure); Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.15～0.4MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%; Adsorbent bed is that activated alumina, silica gel constitute the layering combination cot.
The present invention forms when ring coal gas system methyl alcohol integrated technique and is characterised in that: 2. comprise carbon monodixe conversion part 5100, methane steam transform portion 5200, synthesizing methanol part 5300 from ring coal gas processing part, the hot conversion gas that leaves shift-converter enters the methane steam conversion process and obtains pyrolytic conversion gas, and reforming gas directly enters methanol synthesis reactor with suitable high state of temperature or enters in the methanol synthesis reactor charging.
Compare with conventional charring process, major advantage of the present invention is:
1. because possess the handiness of adjusting virtual oxygen donator oxygen concentration in combustion chamber and virtual fuel body heat value, therefore significantly strengthened the turndown ratio and the stability of charring process;
2. because possess the handiness of adjusting virtual oxygen donator oxygen concentration in combustion chamber and virtual fuel body heat value, therefore significantly strengthened the adaptability of charring process, can enlarge charring process feed coal source, enlarged the charring process range of application the raw material coal;
3. oxygen-enriched combusting has been realized in the combustion chamber, realized poor nitrogenize from ring coal gas, good from ring gas composition PSA separation performance, can significantly reduce adsorptive pressure, significantly reduce the sorbent material consumption, significantly provide component recovery, significantly reduce compression power consumption, form from ring coal gas and utilize chemical industry type technology;
4. be suitable for doing methanol feedstock gas from ring coal gas, can form crude gas transformation and conversion gas system methyl alcohol integral process.
The present invention can realize following comprehensive purpose in the occasion of producing the high-purity hydrogen product:
1. with the combustion chamber temperature control component nitrogen in the conventional coal carbonization technology, partly or entirely by CO
2Component replaces, and under the prerequisite that is not changing existing charing device structure and operational condition substantially, has created precondition for oxygen enrichment or pure oxygen charring process, and the carbonization process gained is poor nitrogen coal gas from ring coal gas; For the denitrogen process of poor nitrogen coal gas, because reduced nitrogen amount, the active principle loss that denitrogen causes can reduce significantly, as the oxygen enrichment and the CO that adopt oxygen volume content 90%
2When preparing virtual oxygen donator, nitrogen can reduce and promptly only is below 5% of air oxygen donator more than 95% in ring coal gas, and the active principle loss that denitrogen causes can reduce 95%, and this is huge improvement;
2. use and return stove CO2 circulation gas, can obtain following purpose:
A, make wherein charcoal three hydrocarbon, ethene, directly be converted into H as fuel
2O, CO
2, use its combustion heat to finish these component utilizations, changed raw gas component distributed number, H
2O obtains separating CO by cooling condensation
2Separated in the decarburization part, finished and the separating of other component;
B, CO
2Circulation gas takes off CO
2Coal gas has constituted CH
4-CO-H
2The main body components system;
C, carbon dioxide component is carried dense, the carbon dioxide enriched stripping gas that obtains is convenient to further utilization (such as making technical pure carbon dioxide or food-grade carbon-dioxide gas);
D, preparation phenol sodium decompose system crude phenols carbon dioxide air source: with rich nitrogen of low heat value and carbon dioxide enriched stripping gas mediation gas, or with the suitable high methane gas of gas concentration lwevel;
3. the CO that contains the CO conversion process
2Circulation, decarburization coal gas has constituted CH
4-H
2The main body components system;
4. the CO that contains desulfurization and sulphur conversion process
2Circulation is carried the dense secondary hydrogen sulfide that obtains with depriving hydrogen sulphide, has improved the gas sweetening process efficiency; CO
2Circulation gas has been finished H
2S separates, and finally is converted into elemental sulfur;
5. carrying hydrogen partial carries methane dense, can realize the concrete operations optimization aim in conjunction with particular case: for the hydrocarbon gas/higher conversion gas of non-gas concentration ratio K, can produce tubular oven fuel gas, adopt the high heat value gas mode of movement, set up efficient pipe network delivery system, save related investment; For the conversion gas that the hydrocarbon gas/non-gas concentration ratio K is lower, can produce the combustion chamber fuel gas of band heat storage, improve energy recovery rate (reduction rate of energy loss);
6. nitrogen component is carried densely, with the methane component relative separation, the rich nitrogen of the low heat value that obtains can be used as low calorie fuels gas or making nitrogen by pressure swing adsorption unstripped gas (obtaining high performance fuel gas simultaneously);
7. in order further to reduce combustion chamber temperature control component CO
2Quantity is utilized the CO in the gas making part internal recycle raw gas
2Component: the partitioning cycle raw gas obtains rich co2 gas and enters charring furnace combustion chamber participation combustion processes.
8. set up gas making portion C O
2The component internal recycle, can be in raw gas Separation and Recovery moisture (can reduce the tar sewage burning amount that contains, significantly fuel saving tolerance) with work and rest Jiao Shui.
9. set up gas making portion C O
2The component internal recycle can reduce non-combustibleconstituents concentration in the raw gas to greatest extent, reduces CO in the raw gas product to greatest extent
2(limiting case is only to comprise the charring furnace process combustion to produce CO to quantity
2Quantity);
10. can directly utilize other hot CO
2Gas recovery heat energy perhaps utilizes charcoal processing to reproduce the CO that device of air exists
2Other logistics heat energy of gas recovery, fuel saving consumption, the output of raising product such as methane gas.
Typically used of the present invention is:
1. transform existing apparatus, realize that oxygen-enriched combusting and coal gas efficiently utilize;
2. form high performance fuel gas production technique, promptly produce low nitrogen coal gas and do uses such as system fuel;
3. form the technology of taking product with hydrogen, Sweet natural gas (methane gas) as the leading factor, Sweet natural gas is defeated outward;
4. form maximum and produce the technology of hydrogen, hydro carbons that coking chamber produces is made combustion chamber main fuel gas;
5. form the technology of producing methanol feedstock gas, form crude gas transformation and conversion gas system methyl alcohol integral process.
Compare with the coal gas complete processing of conventional charring process, operational condition of the present invention can be made following aspect and optimize and revise:
1. for containing the occasion that hydrogen is purified, the carbon monodixe conversion process, take off CO
2Process can adopt lower pressure, reduces non-hydrogen component compression work;
2. for containing the occasion that hydrogen is purified, Hydrogen upgrading process can adopt lower pressure, reduces non-hydrogen component compression work.
The part or all of CO of the present invention
2The heat-carrying component can be the hot gas from other technological process.
The part or all of CO of the present invention
2The heat-carrying component can be the compressed gas from other technological process.
The present invention can be with part or all of CO
2The hot gas of gained enters the combustion chamber after the high-temperature flue gas heat exchange of heat-carrying component and boiler.
The present invention can be with part or all of CO
2The hot gas of gained enters the combustion chamber after heat-carrying component and the heat exchange of sulfur recovery facility high-temperature tail gas.
The part or all of CO of the present invention
2The heat-carrying component is the CO from coal preparing natural gas process
2Discharging gas.
Reference examples
" is that raw material is at the special-purpose blue charcoal of vertical retort refining iron alloy with non-caking coal or weakly caking coal lump coal " technology and equipment of Anshan Thermal Energy Inst. of China Steel Group, employing is suitable coal source with China Datong District, the geographic coal in refreshing mansion, employing is refined blue charcoal and is refined blue charcoal and by-product raw gas and middle coalite tar in vertical retort, this technology has the general feature of similar blue charcoal technology: be the main heat-carrying component of combustion processes with nitrogen.In the representative data of this reference examples, unit scale is 600,000 tons/year of blue charcoal production capacities, and year is 7920 hours/year (330 days date manufactured meter per year) when going into operation, and is raw material with Yulin city Shenmu County's coal, coal gas production capacity 1.03 * 10
9Mark cubic meter/year, 60,000 tons/year of tar production capacities.
1. typical feed coal character is as follows:
With the report of Shenmu County's coal analysis, design is as follows with the ature of coal requirement of coal to upright furnace:
It is the lump coal of 25～80mm that the used feed coal of the blue charcoal of internal thermal upright carbonization furnace production requires, and project is the screening of feed coal with due regard to, and daily requirement coal amount is 3000t/d, i.e. 125t/h.
One group of typical feed coal ature of coal survey report of table 10
| Sequence number | Interventions Requested | Check data | The employing standard |
| 1 | Total water (%) | 10.8 | GB/T211-1996 |
| 2 | Analysis moisture (%) | 3.74 | GB/T212-2001 |
| 3 | Ash content (%) | 4.92 | GB/T212-2001 |
| 4 | Volatile matter (%) | 34.40 | GB/T212-2001 |
| 5 | Characteristic of char residue (1-8) | 2 | GB/T212-2001 |
| 6 | Fixed carbon (%) | 60.04 | GB/T212-2001 |
| 7 | Full sulphur (%) | 0.21 | GB/T214-1996 |
| 8 | Hydrogen richness (%) | 3.69 | GB/T476-2001 |
2. the blue charcoal of major product, have excellent properties such as low ash, low-sulfur, low aluminium, hyperergy, high specific resistance, can be widely used in industries such as iron alloy, calcium carbide, synthetic ammonia and blast furnace blowing, field such as civilian, can partly replace coking coal, gasification briquette and smokeless piece etc., realize resource rational utilization;
Blue carbon yield 600,000 t/a
Wherein: specification 1: 〉=5mm, 520000t/a, specification 2:＜5mm, 80000t/a
Blue charcoal＞5mm grade can supply domestic ferroalloy works, calcium carbide factory, fertilizer plant and outlet;
Coke powder＜5mm can use or power plant for self-supply's usefulness for Steel Plant's blast furnace blowing.
3. coalite tar in one of byproduct is the coal process macromolecular organic compound that Pintsch process produced.Because of the cracking temperature of coal in the upright furnace relatively low, in coalite tar character better and be rich in lower boiling phenol, it is the petroleum products surrogate that non-phenol distillate is easy to hydrocracking, and residual oil (or claiming coal-tar pitch) can coking hot-work be coke and coking distillate (making hydrogenating materials);
Coal tar output 60000t/a, its main character sees Table 11.
The main character of table 11 coal tar
| ? | Density g/cm 3 | Ash content % | Moisture % | Viscosity E 80 |
| Coal tar | ～1.05 | 0.02～0.2 | ≤4 | 2～10 |
Coal tar belongs to semi coking tar, contains cuts such as light oil, creosote and pitch, is mainly used in to produce oil fuel, linkrusta, carbon black and general carbon product.
The results of elemental analyses (%) of table 12 shenfu coal upright furnace coking gained coal tar
| Sample | C | H | N | O | S | The H/C atomic ratio | Remarks |
| Shenfu coal tar 1# | 86.28 | 8.31 | 1.11 | 3.86 | 0.36 | 1.16 | ? |
| Shenfu coal tar 2# | 86.03 | 8.45 | 1.14 | 3.93 | 0.45 | 1.18 | ? |
The main character of table 13 shenfu coal upright furnace coking gained coal tar
4. a large amount of coal gas of by-product, a part is used as coking chamber heat-carrying component, a part is as the combustion chamber fuel of charring furnace, has part not through the combustion chamber but burn in coking chamber charing section through the coal gas of coking chamber cold charcoal section, the present invention supposes that for the simplification problem combustion reactions does not take place charring furnace coking chamber part.
The coal gas that charring furnace produces, a part is made fuel for charring furnace, and a part of coked waste water that supplies burns usefulness, and residual gas is defeated outward with being used as fuel and hydrogen feedstock.
Table 14 reference examples raw gas purposes
| Sequence number | Name of material | Nm 3/a | Ten thousand Nm 3/h |
| 1 | The coal gas ultimate production | 1.03×10 9 | 13.0050 |
| 2 | Purposes 1: upright furnace internal recycle | 5.15×10 8 | 6.5025 |
| 3 | Purposes 2: the outer confession | 5.15×10 8 | 6.5025 |
Table 15 reference examples logistics data
5. project content: the type of furnace is selected ZNZL3082 type internal thermal upright stove for use, and stove group scale is 8 * 8 holes, and corresponding auxiliary facility has fully coal, sieve storage Jiao, charing, bulging cold, sewage disposal and public utility etc.
6. production workshop section
The technological process of production comprises coal workshop section, charing workshop section, the burnt workshop section of sieve fortune, the cold workshop section of drum and sewage disposal workshop section fully.
Charing workshop section: vertical retort takes many grate furnaces body to arrange.The type of furnace is chosen as ZNZL3082 type internal thermal upright carbonization furnace.Furnace binding and characteristics:
● this type of furnace has enlarged heat size than general upright carbonization furnace, and coking chamber length is increased to 3000～3500mm by 2100mm, and height is increased to 8200mm by 7000mm, thereby provides favourable condition for the stable and high yields of upright carbonization furnace.
● increased the volume of combustion chamber and suitably increased air inlet port quantity, coal gas and air are fully burnt in the combustion chamber, hot waste gas evenly enters coking chamber, thereby prevents degrading of dross and inlet mouth effectively.
● coking chamber both sides, every hole are respectively equipped with two-layer totally 4 independently horizontal quirks (combustion chamber) up and down, and the temperature distribution that can regulate every hole coking chamber is neatly guaranteed whole stove uniform in quality, stable.
● the steam quenching is carried out in blue charcoal quenching earlier, carries out the water quenching then.Hydrogen richness makes blue carbonaceous amount increase simultaneously in the main raising coal gas.
● blue charcoal is discharged from upright furnace by the scraper plate machine, is transported to after the oven dry of drying machine and carries out classification on the sieve apparatus, and the blue charcoal after the classification is transported to storage Jiao Chang respectively by conveyor drive.
The technical process of gas purification workshop section: the coal gas → pneumatic trough → gas-liquid separator → direct-cooled one section tower → direct-cooled two sections tower → gas fans → electrical tar precipitator → part coal gas internal recycle that comes out from charring furnace returns outside charring furnace, the part coal gas and supplies the user.
Sewage disposal workshop section: industrial sewage adopts burning disposal, can accomplish the industrial sewage zero release.
7. produce the adjusting characteristics
Existing blue charcoal Design of device thought is to be that major product, coal tar and raw gas are byproduct with blue charcoal, and the main project of production control is into the up to standard and raw gas requisite quality of charcoal speed carbonaceous amount up to standard, blue, and (calorific value is between 1600～2400KCAL/Nm
3).
Embodiment one
Based on reference examples, combustion chamber temperature control component N
2All according to " wait heat-capacity flowrate replace " notion by CO
2Replace, adopt pure oxygen burning, oxygen concentration is 21% in the virtual oxygen donator, supposes that other effect is constant in the charring furnace, and then the variation of raw gas composition sees Table 16.Raw gas belongs to CO before transforming
2-CH
4-CO-N
2-H
2System is transformed the back raw gas and is belonged to CO
2-CH
4-CO-H
2Its CO conversion gas of system then belongs to CO
2-CH
4-H
2System; the a part of raw gas that goes out the charring furnace raw gas returns charring furnace and uses (a part of as internal recycle coking chamber heat-carrying component; a part is as internal recycle fuel gas); all the other efflux raw gas (superfluous raw gas) and purify part and finish depriving hydrogen sulphide and handle and CO conversion process (CO interconversion rate 95%) effluxing raw gas, and conversion gas passes through the rich CO that decarburization partly obtains
2Gas, part circulation return the combustion chamber and constitute " combustion chamber temperature control component CO
2" outer circulation, a part effluxes (discharges the CO that combustion processes produces
2Gas), the decarburization purified gas passes through hydrogen and the high performance fuel gas that hydrogen purification partly obtains.
Table 16 embodiment one logistics data
Form " combustion chamber temperature control component CO
2" the rich CO of outer circulation
2Gas, bring into the combustion chambers burn heat release such as a spot of hydrogen sulfide in the conversion gas, carbon three hydrocarbon, ethene and finish separation and utilization, reduction reaction takes place in charring furnace the oxide compound of hydrogen sulfide becomes hydrogen sulfide, finally is absorbed and can be exchanged into sulphur at ammonia scrubbing and process of wet desulphurization.
" combustion chamber temperature control component CO is provided
2" rich CO
2Gas can be above-mentioned gas, also can be the rich CO from other device (non-blue charcoal device)
2Gas is such as the rich CO of coal preparing natural gas device discharge
2Gas, this richness CO
2Gas can with other hot logistics heat exchange of factory after enter the combustion chamber with the fuel saving consumption.This combustion chamber temperature control component CO
2Quantity 14652Nm
3/ H, 200 ℃ of 40 ℃ to 240 ℃ temperature difference, 1,000,000 kilocalories of heat 14652 * 200 * 0.43=1.26/time, benefit is huge, this richness CO
2Gas can be used as and reclaims heat energy carrier and use, such as can with hot flue gas or other hot logistics heat exchange.
Contrast as can be seen from table 15, table 16, transform the back and be reduced to 86.5%, can reduce from ring coal gas system equipment size from ring coal gas volume.
Embodiment one has described the simple and clear modification scheme to existing apparatus, has changed from ring coal gas to form.
Embodiment one has described the simple and clear modification scheme to existing apparatus, has changed from ring coal gas to form.
Further, will be pressurized to 0.30MPa (absolute pressure) from ring coal gas, through taking off CO
2Part 2008 is separated into internal recycle CO
2Gas (CO
2Quantity 14651.71Nm
3/ h, the rate of recovery 66.3%, purity 97%) and pipe network fuel gas, pipe network fuel gas pressure 0.26～0.27MPa (absolute pressure), variation is compared as follows:
Table 14 reference examples raw gas purposes
The effect that can realize is will be pressurized to 0.30MPa (absolute pressure) from ring coal gas, through taking off CO
2Part 2008 is separated into rich CO
2Gas and pressure are the pipe network fuel gas of 0.26～0.27MPa (absolute pressure), rich CO
2Gas is as internal recycle gas CO
2(CO
2Quantity 14651.71Nm
3/ h, the rate of recovery 66.3%, purity 97%) and efflux CO
2Gas, separating effect is as follows:
Table 15 reference examples raw gas purposes
The above-mentioned CO that takes off
2The sorbent material that part 2008 is used has activated alumina, Kiselgel A.
Embodiment one has constituted simple and clear manufacturing pipe network fuel gas technical process.
Embodiment two
Based on embodiment one, CO is set
2Internal recycle gas will go out the coking chamber raw gas and introduce the PSA1008 part, obtain CO
2Internal recycle gas provides combustion chamber combustion chamber temperature control component CO
2Main body quantity and minute quantity fuel element, insufficient fuel element and CO
2Adapted quantity can provide by the adapted fuel stream, the adapted fuel stream can be come out of the stove raw gas (PSA1008 front portion) or and decarburization raw gas (PSA1008 purified gas), leave above-mentioned CO
2Circulation loop from the ring coal gas, can be come out of the stove raw gas or and the decarburization raw gas.
The present embodiment flow process is as follows: will go out the coking chamber raw gas and be divided into three the tunnel, the first via (main road) is pressurized to 0.20MPa (absolute pressure) (can be lower pressure), through taking off CO
2Part PSA1008 is separated into rich CO
2Gas and pressure are the purified gas of 0.16～0.17MPa (absolute pressure), CO
2Internal recycle gas is as the main body quantity of combustion chamber temperature control component (containing fuel elements such as a spot of carbon three hydrocarbon that might exist, ethene, hydrogen sulfide); The main fuel component is raw gas (be convenient to the Flow-rate adjustment operation, be used to control combustion chamber virtual combustion gas body heat value) the formation fuel element internal recycle of coming out of the stove; The purified gas of PSA1008 part, most of internal recycle gas as coking chamber heat-carrying component, small part purified gas are used as from ring coal gas A.A part is come out of the stove raw gas as from ring coal gas B.From ring coal gas A with from the gas mixture that encircles coal gas B is all from ring coal gas.The above-mentioned CO that takes off
2The sorbent material that part 2008 is used has activated alumina, Kiselgel A.
Table 17 embodiment two logistics data summary sheets one
Embodiment two has constituted simple and clear internal recycle gas making flow process, has formed product hydrogen, producing natural gas technology, and advantage is:
1. reduce non-combustibleconstituents concentration in the raw gas to greatest extent, reduce CO in the raw gas product to greatest extent
2Quantity can be reduced to below 10% even lower usually economically.Present embodiment is considered follow-up have carbon monodixe conversion and conversion qi exhaustion CO
2Step is so comprise whole CO that the charring furnace process combustion produces in ring coal gas
2Quantity;
2. reduce CO to greatest extent
2The working cycle compression work;
3. Separation and Recovery moisture in raw gas simultaneously can reduce the tar sewage burning amount that contains with work and rest Jiao Shui, remarkable fuel saving tolerance, and 3.734 tons of this routine Separation and Recovery moisture/time.
3.734 in ton/time, contain tar sewage as burning, need about 500 ten thousand kilocalories of heat supply/hour, the fuel gas 2884 that consumes calorific value 1935 kilocalorie/mark cube fuel gas is marked cubic meters/hour, energy consumption is huge.
Table 18 embodiment two logistics data summary sheets two
Embodiment three
Based on embodiment two, the internal recycle loop is set, the internal recycle loop is provided with the PSA1008 part, and the PSA1008 stripping gas forms CO
2Internal recycle provides combustion processes thermophore component, PSA1008 purifies coal gas and is divided into internal recycle gas (design objective is as coking chamber heat-carrying component and the possible combustion components of coking chamber) and from ring coal gas, enters conversion gas transformation fractionation by adsorption part 2008 (working pressure 0.3～0.5MPa (absolute pressure), stripping gas CO from ring coal gas through carbon monodixe conversion step 2100 (working pressure 0.4～0.6MPa (absolute pressure), oxygen removal rate 100%, organic sulfur removal rate 90%, carbon monodixe conversion rate 95%)
2Purity 97%, stripping gas CO
2Yield 92%) and 2009 (working pressure 0.8～1.2MPa (absolute pressure), product H
2Purity 99.9%, product H
2Yield 95%) is separated into rich CO
2Gas, methane gas, hydrogen, partly or entirely methane gas enters the combustion chamber and constitutes the fuel gas outer circulation, and during the methane gas output fluctuation, methane tolerance needs to use the part raw gas after a little while or makes postcombustion from ring coal gas and use in the actual production.The rich CH of this scheme
4Gas replaces coal gas (target is the hydrogen in the coal gas) to make fuel gas, can increase hydrogen output.H in embodiment two fuel gas
2With CO flow 4246Nm
3/ h, the hydrogen volume yield calculates by 90%, can increase production hydrogen 3821Nm
3/ h, hydrogen make hydrogenating materials and make the fuel price differential by 1 yuan/Nm
3Calculate, 3821 yuan of price differentials/time, 3,026 ten thousand yuan/year of year price differentials, benefit is huge.
Simultaneously, reduce the about 0.747t/h of output of water, can reduce and contain tar sewage quantity 0.747t/h, energy-saving effect is remarkable.0.747t/h sewage as burn to need about 100 ten thousand kilocalories of heat supply/hour, the fuel gas 568 that consumes calorific value 1935 kilocalorie/mark cube fuel gas is marked cubic meters/hour.
This example has formed maximization and has produced hydrogen technology.
Present embodiment conversion qi exhaustion CO
2Part 2208 stripping gass are preferentially as combustion chamber temperature control component, and the insufficient section of combustion chamber temperature control component uses the PSA1008 stripping gas to form CO
2Internal recycle provides.
Present embodiment as required, can provide some oxygenants (pure oxygen) to coking chamber.
Embodiment four
Based on embodiment one or embodiment two or embodiment three, the pure oxygen burning charring process changes oxygen enrichment (oxygen content 95%) burning carbonate technology into.
At the thick oxygen device of system, air compression is boosted to 0.125～0.150MPa (absolute pressure), during absorption working condition, air passes adsorbent bed based on the lithium dimer sieve, N in the air
2Be adsorbed, oxygen components self-absorbent bed exit end becomes oxygen enrichment, under the selected operational condition, oxygen yield 55～60%, oxygen enrichment carrier of oxygen volume concentrations general common more than 85%, general more than 90%, can reach 93%, oxygen-enriched purity improves, and oxygen recovery rate descends, and the unstripped gas total amount increases.
Although this paper only enumerates four embodiment, the effect that it shows is present in equally and anyly is suitable for adopting in the coal carbonization process of the present invention.
Claims (57)
1. one kind with CO
2Coal carbonization technology for combustion processes temperature control component is characterized in that comprising following steps:
1. gas making partly comprises charring furnace and coking chamber heat-carrying component internal circulation system, and charring furnace comprises the combustion chamber of fuel gas and the coking chamber of coal;
In coking chamber, according to the advance route of coal charge, being divided into first section is that coal preheating section (or claim gas cooling section), second section are that coal carbonization section, the 3rd section are charcoal cooling section (or claiming gas preheating section); In the 3rd section zone, comprise the first via gas of coking chamber heat-carrying component and two sections process material contact heat-exchangings and reclaim and become three sections process gas after its heat heats up, three sections process material leave three sections zones; In second section zone, gas fume of combustion chamber, three sections process gas carry out gas-solid with one section process material and directly contact generation charing effect, and two sections process material leave second section zone and enter the 3rd section zone, and two sections process gas leave second section zone and enter first section zone; In first section zone, after transmitting the heat cooling and sneak into one section generation gas with the outside certainly coal charge Contact Heating coal charge that adds, two sections process gas become one section product gas (raw gas), and become one section process material after coal charge heats up and enter second section zone;
At least a portion is returned coking chamber as coking chamber heat-carrying component based on the logistics of raw gas, constitutes gas making part coking chamber heat-carrying component internal recycle;
Gas making part coal gas product is as leaving the gas making part from ring coal gas;
It is characterized in that: the combustion chamber oxygen donator is oxygen enrichment or pure oxygen, with CO
2Be main combustion chamber temperature control component;
The definition of combustion chamber temperature control component is: from the charring furnace outside, the coexistence of combustion chamber and fuel element, possess the control combustion product gases temperature function, that do not participate in combustion reactions, pass the combustion chamber and pass that coking chamber contacts with coal charge, enter the non-combustibleconstituents in the raw gas when leaving charring furnace.
2. method according to claim 1 is characterized in that:
1. in the gas making part, combustion chamber CO
2The temperature control component ratio of component is greater than 0.50.The definition of combustion chamber temperature control component ratio is: the ratio of specific combustion chamber temperature control component volume and whole combustion chambers temperature control component volume.
3. method according to claim 2 is characterized in that:
1. in the gas making part, combustion chamber CO
2The temperature control component ratio of component is greater than 0.85.
4. method according to claim 2 is characterized in that:
1. in the gas making part, combustion chamber CO
2The temperature control component ratio of component is greater than 0.95.
5. method according to claim 2 is characterized in that:
1. in the gas making part, combustion chamber CO
2The temperature control component ratio of component is greater than 0.50, and the combustion chambers burn flue-gas temperature finally satisfies coking chamber charing section temperature index: lump coal is heated to the expection carbonization temperature by this section.
6. method according to claim 2 is characterized in that:
1. in the gas making part, combustion chamber CO
2The temperature control component ratio of component is greater than 0.85, and the combustion chambers burn flue-gas temperature finally satisfies coking chamber charing section temperature index: lump coal is heated to 600～850 ℃ by this section.
7. method according to claim 2 is characterized in that:
1. in the gas making part, combustion chamber CO
2The temperature control component ratio of component is greater than 0.90, and the combustion chambers burn flue-gas temperature finally satisfies coking chamber charing section temperature index: lump coal is heated to 750～850 ℃ by this section.
8. method according to claim 2 is characterized in that:
1. in the gas making part, combustion chamber CO
2The temperature control component ratio of component is greater than 0.95, and the combustion chambers burn flue-gas temperature finally satisfies coking chamber charing section temperature index: lump coal is heated to 780～820 ℃ by this section.
9. method according to claim 2 is characterized in that:
1. in the gas making part, combustion chamber CO
2The temperature control component ratio of component is greater than 0.50, and the combustion chambers burn flue-gas temperature is 600～900 ℃.
10. method according to claim 2 is characterized in that:
1. in the gas making part, combustion chamber CO
2The temperature control component ratio of component is greater than 0.85, and the combustion chambers burn flue-gas temperature is 700～900 ℃.
11. method according to claim 2 is characterized in that:
1. in the gas making part, combustion chamber CO
2The temperature control component ratio of component is greater than 0.90, and the combustion chambers burn flue-gas temperature is 750～850 ℃.
12. method according to claim 2 is characterized in that:
1. in the gas making part, the whole feeding gas in combustion chamber satisfy following provisions:
The whole feeding gas in combustion chamber are divided into virtual oxygen donator and virtual fuel body;
Virtual oxygen donator is by oxygen components and the CO of first part
2Component constitutes, the CO of first part
2The ratio of component volume amount and oxygen components volume amount calculates (being that the oxygen components volumetric concentration is 16～40% in the virtual oxygen donator), CO by 1.50～5.25
2The temperature control component ratio of component is greater than 0.50;
Virtual fuel body volume calorific value is 1400～2600KCAL/Nm
3
13. method according to claim 2 is characterized in that:
1. in the gas making part, the whole feeding gas in combustion chamber satisfy following provisions:
The whole feeding gas in combustion chamber are divided into virtual oxygen donator and virtual fuel body;
Virtual oxygen donator is by oxygen components and the CO of first part
2Component constitutes, the CO of first part
2The ratio of component volume amount and oxygen components volume amount calculates (being that the oxygen components volumetric concentration is 21～35% in the virtual oxygen donator), CO by 1.85～3.76
2The temperature control component ratio of component is greater than 0.90;
Virtual fuel body volume calorific value is 1700～2400KCAL/Nm
3
14. method according to claim 2 is characterized in that:
1. in the gas making part, raw gas enters transformation fractionation by adsorption part PSA1008 after at least a portion de-oiling, and during absorption working condition, raw gas passes when adsorbent bed after the de-oiling, sorbent material selective adsorption CO
2And the easier component that is adsorbed, H
2, CH
4, component such as CO passes adsorbent bed becoming and takes off CO
2Coal gas; At least a portion is taken off CO
2Coal gas returns the charring furnace coking chamber as coking chamber heat-carrying component, forms coking chamber heat-carrying component internal recycle gas; During the desorb operating mode, obtain rich CO
2Gas, the rich CO of at least a portion
2Gas returns the charring furnace combustion chamber combustion chamber temperature control component is provided, and forms combustion chamber temperature control component internal recycle gas; Do not return the coal gas (raw gas and or take off CO of charring furnace in gas making part
2Coal gas) be used as from ring coal gas.
15., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 described methods:
1. in the gas making part, isolate rich CO based on the logistics employing variable-pressure adsorption separating method of de-oiling raw gas
2Gas, the rich CO of at least a portion
2Gas returns the charring furnace combustion chamber combustion chamber temperature control component is provided, and forms combustion chamber temperature control component internal recycle gas.
16., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 described methods:
1. in the gas making part, adopt variable-pressure adsorption separating method to isolate based on the logistics of de-oiling raw gas and take off CO
2Coal gas, at least a portion is taken off CO
2Coal gas returns the charring furnace coking chamber coking chamber heat-carrying component is provided, and forms coking chamber heat-carrying component internal recycle gas.
17., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 described methods:
2. from ring coal gas processing part, adopt variable-pressure adsorption separating method to isolate rich CO based on logistics from ring coal gas
2Gas WH, at least a portion WH return the charring furnace combustion chamber and make combustion chamber temperature control component, form combustion chamber temperature control component outer circulation gas.
18., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 described methods:
2. from ring coal gas processing part, adopt variable-pressure adsorption separating method to isolate poor H based on logistics from ring coal gas
2, poor CO
2Gas returns the charring furnace combustion chamber combustion chamber fuel element is provided, and forms combustion chamber fuel element outer circulation gas.
19. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 described methods, form and produce high performance fuel gas technology, it is characterized in that:
1. in the gas making part, raw gas enters transformation fractionation by adsorption part PSA1008 after the de-oiling, during absorption working condition, after the de-oiling raw gas pass adsorbent bed, sorbent material selective adsorption CO
2And the easier component that is adsorbed, H
2, CH
4, component such as CO passes the adsorbent bed high heating value gas that becomes.
20. method according to claim 19 forms and produces high performance fuel gas technology, it is characterized in that:
1. in the gas making part, a part of high heating value gas returns the charring furnace coking chamber, as coking chamber heat-carrying component, forms coking chamber heat-carrying component internal recycle gas.
21. method according to claim 19 forms and produces high performance fuel gas technology, it is characterized in that:
1. the operational condition of transformation fractionation by adsorption separate part PSA1008 is: adsorption process pressure is between 0.13～0.5MPa (absolute pressure); During the drop pressure end of processing, adsorption column pressure is between 0.07～0.13MPa (absolute pressure); The reverse step that vacuumizes is when finishing, and adsorption column pressure is between 0.003～0.03MPa (absolute pressure); Adsorbent bedly constitute layering combination cot, the CO of purified gas for a kind of in the activated alumina, gac, silica gel or by wherein several
2Volumetric concentration is less than 15%, and stripping gas carbonic acid gas volumetric concentration is greater than 90%.
22. method according to claim 21 forms and produces high performance fuel gas technology, it is characterized in that:
1. the operational condition of transformation fractionation by adsorption separate part PSA1008 is: adsorption process pressure is between 0.15～0.3MPa (absolute pressure); Adsorbent bed is the layering combination cot that activated alumina, silica gel constitute, the CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%.
23. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 described methods, form and produce high performance fuel gas technology, it is characterized in that:
1. in the gas making part, raw gas enters transformation fractionation by adsorption part PSA1008 after the de-oiling, and during absorption working condition, raw gas passes when adsorbent bed after the de-oiling, sorbent material selective adsorption CO
2And the easier component that is adsorbed, H
2, CH
4, component such as CO passes the adsorbent bed high heating value gas that becomes, partly or entirely stripping gas returns the charring furnace combustion chamber, and combustion chamber temperature control component is provided, and forms combustion chamber temperature control component internal recycle gas.
24. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 described methods, form, it is characterized in that from ring gas production hydrogen and fuel gas technology:
2. comprise hydrogen purification part PSA2089 from ring coal gas processing part;
In the PSA2089 part, during absorption working condition, unstripped gas passes when adsorbent bed, and sorbent material selective adsorption non-hydrogen components, hydrogen component are passed the adsorbent bed PSA2089 of becoming purified gas, and the PSA2089 stripping gas is as fuel gas.
25. method according to claim 24 forms from ring gas production hydrogen and fuel gas technology, it is characterized in that:
1. the operational condition of PSA2089 is: adsorption process pressure is between 0.5～2.5MPa (absolute pressure); During the drop pressure end of processing, adsorption column pressure is between 0.25～0.40MPa (absolute pressure); When reverse deflation course finished, adsorption column pressure was between 0.13～0.15MPa (absolute pressure); Adsorbent bedly constitute layering combination cot, the H of purified gas for a kind of in the gac, silica gel, zeolite molecular sieve or by wherein several
2Volumetric concentration is greater than 95%, H
2The volume yield is greater than 92%.
26. method according to claim 25 forms from ring gas production hydrogen and fuel gas technology, it is characterized in that:
2. the operational condition of PSA2089 is: adsorption process pressure is between 0.6～1.5MPa (absolute pressure); The reverse VC step that vacuumizes is when finishing, and adsorption column pressure is between 0.02～0.05MPa (absolute pressure); The H of purified gas
2Volumetric concentration is greater than 99%, H
2The volume yield is greater than 90%.
27. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 described methods, form, it is characterized in that from ring gas production hydrogen and fuel gas technology:
2. comprise from ring coal gas processing part and take off CO
2Part PSA2008 and hydrogen purification part PSA2009;
In the PSA2008 part, during absorption working condition, unstripped gas passes when adsorbent bed, sorbent material selective adsorption CO
2And the easier component that is adsorbed, H
2, CH
4, component such as CO passes the adsorbent bed PSA2008 of becoming purified gas, at least a portion PSA2008 stripping gas returns the charring furnace combustion chamber, and combustion chamber temperature control component is provided, and forms combustion chamber temperature control component outer circulation gas;
In the PSA2009 part, during absorption working condition, unstripped gas passes when adsorbent bed, and sorbent material selective adsorption non-hydrogen components, hydrogen component are passed the adsorbent bed PSA2009 of becoming purified gas, and the PSA2009 stripping gas is as high methane gas.
28. method according to claim 27 forms and produces high performance fuel gas technology, it is characterized in that:
1. take off CO
2The operational condition of part PSA2008 is: adsorption process pressure is between 0.2～0.8MPa (absolute pressure); During the drop pressure end of processing, adsorption column pressure is between 0.07～0.13MPa (absolute pressure); The reverse VC step that vacuumizes is when finishing, and adsorption column pressure is between 0.003～0.03MPa (absolute pressure); Adsorbent bedly constitute layering combination cot, the CO of purified gas for a kind of in the activated alumina, gac, silica gel or by wherein several
2Volumetric concentration is less than 15%, and stripping gas carbonic acid gas volumetric concentration is greater than 90%;
The operational condition of hydrogen purification part PSA2009 is: adsorption process pressure is between 0.5～2.5MPa (absolute pressure); During the drop pressure end of processing, adsorption column pressure is between 0.25～0.40MPa (absolute pressure); When reverse deflation course finished, adsorption column pressure was between 0.13～0.15MPa (absolute pressure); Adsorbent bedly constitute layering combination cot, the H of purified gas for a kind of in the gac, silica gel, zeolite molecular sieve or by wherein several
2Volumetric concentration is greater than 95%, H
2The volume yield is greater than 90%.
29. method according to claim 27 forms and produces high performance fuel gas technology, it is characterized in that:
2. comprise carbon monodixe conversion part 2100 from ring coal gas processing part and take off CO
2Part PSA2008 and hydrogen purification part PSA2009;
Carbon monodixe conversion hydrogen manufacturing part 2100 operational conditions are: the carbon monoxide transformation efficiency greater than 85%, oxygen all transforms, the organosulfur transformation efficiency is greater than 85%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.8MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that the molecular ratio of 300～2500 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide is 1.3～6.0 that average reaction temperature is lower than 350 ℃, pressure; Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA2008;
Take off CO
2The operational condition of part PSA2008 is: adsorption process pressure is between 0.2～0.7MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%;
The operational condition of hydrogen purification part PSA2009 is: adsorption process pressure is between 0.6～1.5MPa (absolute pressure); The reverse VC step that vacuumizes is when finishing, and adsorption column pressure is between 0.02～0.05MPa (absolute pressure); The H of purified gas
2Volumetric concentration is greater than 99%, H
2The volume yield is greater than 94%.
30. method according to claim 29 forms and produces high performance fuel gas technology, it is characterized in that:
1. carbon monodixe conversion hydrogen manufacturing part 2100 operational conditions are: the carbon monoxide transformation efficiency greater than 90%, oxygen all transforms, the organosulfur transformation efficiency is greater than 90%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.6MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that 500～2000 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide molecule ratio are 1.5～4.5 that average reaction temperature is lower than 300 ℃, pressure; Enter after conversion gas reduction temperature to the 35～45 ℃ dehydration and take off CO
2Part PSA2008;
Take off CO
2The operational condition of part PSA2008 is: adsorption process pressure is between 0.2～0.5MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%;
The operational condition of hydrogen purification part PSA2009 is: adsorption process pressure is between 0.7～1.2MPa (absolute pressure); The H of purified gas
2Volumetric concentration is greater than 99%, H
2The volume yield is greater than 96%.
31. method according to claim 30 forms and produces high performance fuel gas technology, it is characterized in that:
1. carbon monodixe conversion hydrogen manufacturing part 2100 operational conditions are: the carbon monoxide transformation efficiency greater than 95%, oxygen all transforms, the organosulfur transformation efficiency is greater than 95%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.5MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that 800～1500 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide molecule ratio are 1.5～3.5 that average reaction temperature is lower than 250 ℃, pressure; Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA2008;
The operational condition of transformation fractionation by adsorption separate part PSA2008 is: adsorption process pressure is between 0.15～0.4MPa (absolute pressure); Adsorbent bed is that activated alumina, silica gel constitute layering combination cot, the CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%.
32. method according to claim 27 forms from ring coal gas main product hydrogen technology, it is characterized in that:
2. at hydrogen purification part PSA2009, partly or entirely the PSA2009 stripping gas returns the charring furnace combustion chamber, and the combustion chamber fuel element is provided, and forms combustion chamber fuel element outer circulation gas.
33. method according to claim 28 forms from ring coal gas main product hydrogen technology, it is characterized in that:
2. at hydrogen purification part PSA2009, partly or entirely the PSA2009 stripping gas returns the charring furnace combustion chamber, and the combustion chamber fuel element is provided, and forms combustion chamber fuel element outer circulation gas.
34. method according to claim 29 forms from ring coal gas main product hydrogen technology, it is characterized in that:
2. at hydrogen purification part PSA2009, partly or entirely the PSA2009 stripping gas returns the charring furnace combustion chamber, and the combustion chamber fuel element is provided, and forms combustion chamber fuel element outer circulation gas.
35. method according to claim 30 forms from ring coal gas main product hydrogen technology, it is characterized in that:
2. at hydrogen purification part PSA2009, partly or entirely the PSA2009 stripping gas returns the charring furnace combustion chamber, and the combustion chamber fuel element is provided, and forms combustion chamber fuel element outer circulation gas.
36. method according to claim 31 forms from ring coal gas main product hydrogen technology, it is characterized in that:
2. at hydrogen purification part PSA2009, partly or entirely the PSA2009 stripping gas returns the charring furnace combustion chamber, and the combustion chamber fuel element is provided, and forms combustion chamber fuel element outer circulation gas.
37., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 described methods:
At least a portion provides combustion chamber temperature control component CO
2Logistics and the high-temperature flue gas heat exchange of boiler after the hot gas of gained enter the combustion chamber.
38., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 described methods:
At least a portion provides combustion chamber temperature control component CO
2Logistics and the heat exchange of sulfur recovery facility high-temperature tail gas after the hot gas of gained enter the combustion chamber.
39., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 described methods:
At least a portion provides combustion chamber temperature control component CO
2Logistics be discharging gas from coal preparing natural gas process.
40. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 described methods, form system methanol feedstock gas technology, it is characterized in that:
1. from ring coal gas processing part, at least a portion from ring coal gas as system methanol feedstock gas.
41. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 described methods, form system methanol feedstock gas technology, it is characterized in that:
2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.0～2.5.
42. according to the described method of claim 41, form system methanol feedstock gas technology, it is characterized in that:
2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.5～2.0; Carbon monodixe conversion hydrogen manufacturing part 3100 operational conditions are: the carbon monoxide transformation efficiency is regulated conversion gas H
2/ CO molecular ratio is 1.5～2.5, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that the molecular ratio of 3.0～15MPa (absolute pressure), water vapor/carbon monoxide is 0.7～2.5 that average reaction temperature is lower than 350 ℃, pressure; The hot conversion gas that leaves shift-converter enters methanol sythesis reactor.
43. according to the described method of claim 41, form system methanol feedstock gas technology, it is characterized in that:
2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.5～2.0; Carbon monodixe conversion hydrogen manufacturing part 3100 operational conditions are: the carbon monoxide transformation efficiency is regulated conversion gas H
2/ CO molecular ratio is 1.5～2.5, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that the molecular ratio of 3.0～15MPa (absolute pressure), water vapor/carbon monoxide is 0.7～2.5 that average reaction temperature is lower than 350 ℃, pressure; The hot conversion gas that leaves shift-converter enters in the circulation gas raw material of methanol sythesis reactor.
44. according to the described method of claim 40, form system methanol feedstock gas technology, it is characterized in that:
2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.5～2.0;
Take off the impurity step from ring coal gas through hydrogenation, organosulfur is converted into hydrogen sulfide, oxygen is converted into water, reforming gas is divided into two-way, and first via reforming gas obtains conversion gas, the H of the gas mixture of the conversion gas and the second road reforming gas through carbon monodixe conversion part 3100
2/ CO molecular ratio is 1.5～2.0.
45. according to the described method of claim 44, form system methanol feedstock gas technology, it is characterized in that:
2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.5～2.0; Carbon monodixe conversion hydrogen manufacturing part 3100 operational conditions are: the carbon monoxide transformation efficiency greater than 50%, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that the molecular ratio of 3.0～15MPa (absolute pressure), water vapor/carbon monoxide is 0.7～2.5 that average reaction temperature is lower than 350 ℃, pressure.
46. according to the described method of claim 45, form system methanol feedstock gas technology, it is characterized in that:
2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, carbon monodixe conversion hydrogen manufacturing part 2100 operational conditions are: the carbon monoxide transformation efficiency is greater than 65%.
47. according to the described method of claim 46, form system methanol feedstock gas technology, it is characterized in that:
2. comprise carbon monodixe conversion part 3100 from ring coal gas processing part, carbon monodixe conversion hydrogen manufacturing part 2100 operational conditions are: the carbon monoxide transformation efficiency is greater than 85%.
48. according to the described method of claim 40, form system methanol feedstock gas technology, it is characterized in that:
2. comprise carbon monodixe conversion part 4100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.5～2.0; Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA4108, PSA4108 takes off CO
2Gas is as system methanol feedstock gas.
49. according to the described method of claim 48, form system methanol feedstock gas technology, it is characterized in that:
2. comprise carbon monodixe conversion part 4100 from ring coal gas processing part, its function is to regulate conversion gas H
2/ CO molecular ratio is 1.5～2.0; Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA4108, PSA4108 takes off CO
2Gas is as system methanol feedstock gas;
Carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: the carbon monoxide transformation efficiency is regulated conversion gas H
2/ CO molecular ratio is 1.5～2.0, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.8MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that the molecular ratio of 300～2500 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide is 0.7～2.0 that average reaction temperature is lower than 350 ℃, pressure;
Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.2～0.7MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%.
50. according to the described method of claim 49, form system methanol feedstock gas technology, it is characterized in that:
2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: carbon monoxide transformation catalyst bed working pressure is 0.3～0.6MPa (absolute pressure);
Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.2～0.5MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%.
51. according to the described method of claim 50, form system methanol feedstock gas technology, it is characterized in that:
2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: carbon monoxide transformation catalyst bed working pressure is 0.3～0.5MPa (absolute pressure);
Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.15～0.4MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%; Adsorbent bed is that activated alumina, silica gel constitute the layering combination cot.
52. according to the described method of claim 40, form system methanol feedstock gas technology, it is characterized in that:
2. comprise carbon monodixe conversion part 4100 from ring coal gas processing part, take off the impurity step from ring coal gas through hydrogenation, organosulfur is converted into hydrogen sulfide, oxygen is converted into water, reforming gas is divided into two-way, first via reforming gas obtains conversion gas, the H of the gas mixture of the conversion gas and the second road reforming gas through carbon monodixe conversion part 4100
2/ CO molecular ratio is 1.5～2.0;
Enter after conversion gas reduction temperature to the 30～50 ℃ dehydration and take off CO
2Part PSA4108, PSA4108 takes off CO
2Gas is as system methanol feedstock gas.
53. according to the described method of claim 52, form system methanol feedstock gas technology, it is characterized in that:
2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: the carbon monoxide transformation efficiency is regulated conversion gas H
2/ CO molecular ratio is 1.5～2.0, oxygen all transforms, the organosulfur transformation efficiency is greater than 99%; Carbon monoxide transformation catalyst bed operational condition is: it is that 0.3～0.8MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that the molecular ratio of 300～2500 standard cubic meter unstripped gas/cubic meter catalyzer, water vapor/carbon monoxide is 0.7～2.0 that average reaction temperature is lower than 350 ℃, pressure;
Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.2～0.7MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 10%, and stripping gas carbonic acid gas volumetric concentration is greater than 95%.
54. according to the described method of claim 53, form system methanol feedstock gas technology, it is characterized in that:
2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: carbon monoxide transformation catalyst bed working pressure is 0.3～0.6MPa (absolute pressure);
Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.2～0.5MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%.
55. according to the described method of claim 54, form system methanol feedstock gas technology, it is characterized in that:
2. carbon monodixe conversion hydrogen manufacturing part 4100 operational conditions are: carbon monoxide transformation catalyst bed working pressure is 0.3～0.5MPa (absolute pressure);
Take off CO
2The operational condition of part PSA4108 is: adsorption process pressure is between 0.15～0.4MPa (absolute pressure); The CO of purified gas
2Volumetric concentration is less than 7%, and stripping gas carbonic acid gas volumetric concentration is greater than 97%; Adsorbent bed is that activated alumina, silica gel constitute the layering combination cot.
56. according to the described method of claim 40, form system methyl alcohol integrated technique, it is characterized in that:
2. comprise carbon monodixe conversion part 5100, methane steam transform portion 5200, synthesizing methanol part 5300 from ring coal gas processing part, the hot conversion gas that leaves shift-converter enters the methane steam conversion process and obtains pyrolytic conversion gas, and reforming gas directly enters methanol synthesis reactor with suitable high state of temperature.
57. according to the described method of claim 56, form system methyl alcohol integrated technique, it is characterized in that:
2. reforming gas directly enters in the methanol synthesis reactor charging with suitable high state of temperature.
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| CN113801672A (en) * | 2021-10-25 | 2021-12-17 | 昆明理工大学 | Improved method of internal hot ram charcoal furnace production process based on carbon dioxide protection |
| CN113801672B (en) * | 2021-10-25 | 2024-04-05 | 昆明理工大学 | Method for improving production process of internal thermal semi-coke furnace based on carbon dioxide protection |
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Application publication date: 20110928 |